Stem bases and lead pins for matched-seal glass hermetic seals, as well as hermetic terminals and semiconductor devices.

Abstract

The present invention provides a stem base for a matched-type glass hermetic seal that combines the following characteristics: (i) the base's thermal expansion coefficient in the thickness direction can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby improving the consistency of thermal expansion coefficients with the sealing glass and achieving high bonding reliability with the sealing glass; and (ii) the base has sufficiently high thermal conductivity in the thickness direction. [Solution] A plate-shaped or cylindrical stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. This [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded bodies, and when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction of the base in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure in the horizontal direction of the base in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

Description

[Technical Field]

[0001] The present invention relates to a stem base and lead pins constituting a matched-seal glass hermetic seal, and to a hermetic terminal and semiconductor device equipped therewith. [Background technology]

[0002] A glass hermetic seal is a seal in which a metal lead pin is hermetically sealed through a through-hole in a metal stem base via glass (sealant). It is used, for example, to supply current to electrical equipment or components housed in an airtight container, or to lead signals from electrical equipment or components to the outside. Specific examples include airtight terminals.

[0003] Glass hermetic seals come in two types: compression sealing and conformal sealing. The compression sealing type utilizes the difference in thermal expansion coefficients between the stem base (metal) and the sealing glass, applying compressive stress to the sealing glass and lead pin from the stem base side to mechanically seal the lead pin. In this type, the lead pin and glass are set in the insertion hole of the stem base, the glass is heated and melted, and then cooled and solidified. The difference in contraction between the stem base and the sealing glass causes the stem base to compress the sealing glass and lead pin, mechanically sealing the lead pin.

[0004] On the other hand, in the harmonized sealing type, in order to minimize the difference in shrinkage between the metal stem base and lead pins and the sealing glass, the metal stem base and lead pins and the sealing glass are made of materials with thermal expansion coefficients that are as close as possible (as close as possible in the temperature range from the glass transition temperature to room temperature). In this harmonized sealing type, an oxide film is formed on the surface of the metal (stem base and lead pins) in advance, and this oxide film acts as an adhesive to the sealing glass (chemically reacts with the sealing glass and adheres to it), thereby sealing the lead pins.

[0005] In the compression sealing type, since pressure (compressive stress) is firmly applied to the sealing glass from the stem base side for sealing, there is a problem that it cannot be applied to glass hermetic components where sufficient pressure required for sealing cannot be applied due to their shape. However, in the matching sealing type, such shape constraints are few, and a relatively free design is possible. In conventional matching sealing type glass hermetic seals, it is common to use an Fe-Ni-Co alloy called Kovar for the stem base and lead pins (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the stem base and lead pins of conventional matching sealing type glass hermetic seals have the following technical problems. As described above, an Fe-Ni-Co alloy generally called Kovar is used for the metal side (stem base and lead pins) of the matching sealing type glass hermetic seal. Usually, there is a certain difference in the coefficient of thermal expansion between Kovar and the sealing glass. Therefore, as a matching sealing type glass hermetic seal, it is desirable that the compatibility of the coefficients of thermal expansion between the metal side and the sealing glass be further enhanced, and the bonding reliability and the reliability of airtightness between the metal side and the sealing glass be further improved.

[0008] Furthermore, in the case of semiconductor devices equipped with matched-seal glass hermetic seals (for example, semiconductor packages such as TO headers and hermetic packages for sensors), heat generated from the semiconductor elements needs to be properly dissipated through the stem base. However, the metal material constituting the stem base (generally Kovar is used) has low thermal conductivity, making it difficult to properly dissipate the heat generated from the semiconductor elements. As a result, conventional semiconductor devices have insufficient heat dissipation performance, which can easily lead to problems such as reduced output and shorter lifespan of semiconductor elements, and also make it difficult to accommodate the increasing power output and performance of semiconductor devices.

[0009] Furthermore, if the lead pin has low axial electrical conductivity, it generates more heat when energized, and the amount of heat generated increases with the size of the current flowing through the lead pin. The metal materials conventionally used for lead pins (generally Kovar) have low axial electrical conductivity and cannot adequately suppress the amount of heat generated by the lead pin when energized. For this reason, depending on the type of device equipped with a matched-seal glass hermetic seal, conventionally used lead pins may not be usable. In addition, low electrical conductivity of the lead pin can lead to increased power consumption at the lead pin, resulting in problems such as increased load on the battery. Furthermore, harmonized-seal glass hermetic seals have the drawback of having lower mechanical strength compared to compression-sealed seals, and improvements in this area are desirable to further enhance bonding reliability.

[0010] As described above, the stem base of a matched-type glass hermetic seal is required to have a thermal expansion coefficient in the base thickness direction (however, in the case of a plate-shaped stem base, the thermal expansion coefficient in the plate thickness direction; in the case of a cylindrical stem base, the thermal expansion coefficient in the cylindrical direction; the same applies hereinafter) that is as close as possible to the thermal expansion coefficient of the sealing glass, and to obtain high bonding reliability that can maintain a proper bonding state with the sealing glass for a long period of time, and also to have sufficiently high thermal conductivity in the base thickness direction. Furthermore, the lead pins of a matched-type glass hermetic seal are required to have an axial thermal expansion coefficient as close as possible to the thermal expansion coefficient of the sealing glass, and to obtain high bonding reliability that can maintain a proper bonding state with the sealing glass for a long period of time, and also to have sufficiently high axial electrical conductivity. However, no stem base or lead pins that can satisfy such requirements have been known to date.

[0011] The present invention has been made to solve the problems of the prior art described above, and its objective is to provide a stem base for a matched sealing type glass hermetic seal that has the following characteristics: (i) the base's thermal expansion coefficient in the thickness direction can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby improving the consistency of thermal expansion coefficients with the sealing glass and thus achieving high bonding reliability with the sealing glass; and (ii) the base has a sufficiently high thermal conductivity in the thickness direction. Another object of the present invention is to provide a lead pin for a matched sealing glass hermetic seal that has the following characteristics: (i) its axial thermal expansion coefficient can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby improving the consistency of thermal expansion coefficients with the sealing glass and thus achieving high bonding reliability with the sealing glass; and (ii) its axial electrical conductivity is sufficiently high. Furthermore, another object of the present invention is to provide an airtight terminal and semiconductor device having a stem base and / or lead pins having the above-described excellent properties. [Means for solving the problem]

[0012] As a result of repeated studies to solve the above problems, the inventors of the present invention have obtained the following findings. (I) A metal material obtained by reducing the diameter of a material consisting of a [Cr and / or Mo]-Cu composite obtained by powder metallurgy is subjected to a reduction in surface area (diameter reduction stretching) to stretch it into a rod or wire shape (i.e., a [Cr and / or Mo]-Cu composite that is a diameter reduction stretched material of a powder metallurgy molded body). This material has a metallic structure in which the Cr phase and / or Mo phase are dispersed in a Cu matrix. When the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the stretching direction (axial direction) in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction (radial direction) in which flake-like, small-piece-like, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. While rolled Cr-Cu composite sheets (rolled into a plate shape with a flat roll) are conventionally known, the cross-sectional structure of the above metal material is completely different from that of these rolled Cr-Cu composite sheets.

[0013] (II-1) Metal materials having the above-described cross-sectional structure in the stretching direction and perpendicular to the stretching direction ([Cr and / or Mo]-Cu composites, which are diameter-reduced stretching materials for powder metallurgy molded products; hereinafter sometimes referred to as "these metal materials") have unique properties (characteristics) that differ from those of metal materials (mainly Kovar) conventionally used for stem bases and lead pins of matched-seal glass hermetic seals. In other words, this metal material has the characteristics that thermal expansion in the stretching direction is less than thermal expansion in the direction perpendicular to stretching, meaning that the thermal expansion in the stretching direction is relatively small and isotropic. In its application as a component of matched-seal glass hermetic seals, it has particularly useful and distinctive characteristics, including: (i) the magnitude of thermal expansion in the stretching direction changes depending on the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio when the material is reduced in diameter by reduction processing (diameter reduction stretching). By selecting these blending ratios and reduction ratios, the magnitude of thermal expansion in the stretching direction can be changed (adjusted); and (ii) it has high thermal conductivity and electrical conductivity in the stretching direction. Among these, those with optimized properties have significantly higher thermal conductivity and electrical conductivity in the stretching direction compared to Kovar and other materials widely used in stem bases and lead pins of matched-seal glass hermetic seals. Furthermore, since the magnitude of the electrical conductivity and thermal conductivity in the stretching direction of this metal material changes depending on the reduction ratio during the diameter reduction stretching process, by selecting the reduction ratio, it is possible to change (adjust) not only the magnitude of the thermal expansion coefficient in the stretching direction as described above, but also the magnitude of the electrical conductivity and thermal conductivity in the stretching direction.

[0014] (II-2) Therefore, a stem base composed of a plate-shaped main metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded products) with the above-mentioned stretching direction as the plate thickness direction and the direction perpendicular to the stretching direction as the plate surface direction, or a cylindrical main metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded products) with the above-mentioned stretching direction as the cylindrical axis direction and the direction perpendicular to the stretching direction as the cylindrical diameter direction, is in the base thickness direction (however, in the case of a plate-shaped stem base, the plate thickness direction, and in the case of a cylindrical stem base, the cylindrical axis) Direction. The same applies below.) The thermal expansion coefficient and the thermal expansion coefficient in the horizontal direction of the base (however, in the case of a plate-shaped stem base, the direction of the plate surface, and in the case of a cylindrical stem base, the direction of the cylinder; the same applies below) have the characteristics that the thermal expansion coefficient in the thickness direction of the base < the thermal expansion coefficient in the horizontal direction of the base, that the thermal expansion coefficient in the thickness direction of the base is relatively small, and that the thermal expansion coefficient in the horizontal direction of the base is isotropic. In particular, as useful and characteristic properties for stem bases of matched sealing type glass hermetic seals, they possess the following characteristics (i) and (ii). Note that the plate surface direction above refers to the direction parallel to the plate surface (the same applies below).

[0015] (i) The magnitude of the thermal expansion coefficient in the base thickness direction changes depending on the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio during diameter reduction and stretching of the material. By selecting these blending ratios and reduction ratios, the magnitude of the thermal expansion coefficient in the base thickness direction can be changed (adjusted). Specifically, the higher the blending ratio and the larger the reduction ratio, the smaller the thermal expansion coefficient in the base thickness direction can be. Therefore, depending on the thermal expansion coefficient of the sealing glass used, the thermal expansion coefficient in the base thickness direction can be brought as close as possible to the thermal expansion coefficient of the sealing glass (in some cases, they can be made to almost match), and by improving the consistency of thermal expansion coefficients with the sealing glass, very high bonding reliability with the sealing glass can be obtained. (ii) Those with high thermal conductivity in the base thickness direction, and those with optimized properties, have significantly higher thermal conductivity in the base thickness direction compared to conventional stem bases, which mainly use Kovar.

[0016] Furthermore, the magnitude of the thermal conductivity in the thickness direction of this stem base changes depending on the reduction ratio during the diameter reduction and stretching of the material (the larger the reduction ratio, the greater the thermal conductivity in the thickness direction of the base). Therefore, by selecting the reduction ratio, it is possible to adjust not only the magnitude of the thermal expansion coefficient in the thickness direction of the base as described above, but also the magnitude of the thermal conductivity in the thickness direction of the base. Furthermore, this stem base has a thermal expansion coefficient in the thickness direction less than the thermal expansion coefficient in the horizontal direction of the base, and the horizontal thermal expansion coefficient of the base is isotropic. When the thermal expansion coefficient in the thickness direction of the base is matched to the thermal expansion coefficient of the sealing glass, the horizontal thermal expansion coefficient of the base becomes greater than the thermal expansion coefficient of the sealing glass. Therefore, even though it is a harmonized sealing type glass hermetic seal, compressive stress can be applied to the sealing glass (provided that the shape of the glass hermetic component allows for compressive stress to be applied to the sealing glass). As a result, a harmonized sealing type glass hermetic seal that takes compression sealing into account can be constructed, increasing the mechanical strength of the seal, and thus further improvement in the reliability of the bond with the sealing glass can be expected.

[0017] (II-3) Furthermore, lead pins made of this metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded products) in the shape of a rod or wire with the above-mentioned stretching direction as the axial direction and the direction perpendicular to the stretching direction as the radial direction have the characteristics that the axial thermal expansion coefficient is less than the radial thermal expansion coefficient, and that the axial thermal expansion coefficient is relatively small and the radial thermal expansion coefficient is isotropic. In particular, they possess the following characteristics (i) and (ii) which are useful and characteristic for lead pins of matched sealing type glass hermetic seals. (i) The magnitude of the axial thermal expansion coefficient changes depending on the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio during the reduction of diameter of the material due to the reduction of diameter (reduced diameter stretching process). By selecting these blending ratios and reduction ratios, the magnitude of the axial thermal expansion coefficient can be changed (adjusted). Specifically, the higher the blending ratio and the larger the reduction ratio, the smaller the axial thermal expansion coefficient can be. Therefore, depending on the thermal expansion coefficient of the sealing glass used, the axial thermal expansion coefficient can be brought as close as possible to the thermal expansion coefficient of the sealing glass (in some cases, it can be made to almost match), and by improving the consistency of thermal expansion coefficients with the sealing glass, very high bonding reliability with the sealing glass can be obtained. (ii) Those with high axial electrical conductivity, and especially those with optimized characteristics, have significantly higher axial electrical conductivity compared to conventional lead pins, which mainly use Kovar. Furthermore, the magnitude of the axial electrical conductivity of this lead pin changes depending on the reduction ratio during the diameter reduction and stretching of the material (the larger the reduction ratio, the greater the axial electrical conductivity). Therefore, by selecting the reduction ratio, it is possible to adjust not only the magnitude of the axial thermal expansion coefficient mentioned above, but also the magnitude of the axial electrical conductivity.

[0018] (II-4) Furthermore, as described above, the stem base described in (II-2) can have its thermal expansion coefficient in the base thickness direction changed (adjusted), and the lead pin described in (II-3) can have its axial thermal expansion coefficient changed (adjusted). Therefore, when this metal material is used for one of the stem base or lead pin components of a harmonized glass hermetic seal, the other component can be made from a metal material that has not been conventionally used in harmonized glass hermetic seals (for example, Ni-Fe material or carbon steel). For example, when this metal material is used for the stem base and Ni-Fe material is used for the lead pin, a sealing glass with a thermal expansion coefficient corresponding to Ni-Fe material should be used, and the thermal expansion coefficient of the stem base made of this metal material should be matched to the thermal expansion coefficient of this sealing glass. Alternatively, when carbon steel is used for the stem base and this metal material is used for the lead pin, a sealing glass with a thermal expansion coefficient corresponding to carbon steel should be used, and the axial thermal expansion coefficient of the lead pin made of this metal material should be matched to the thermal expansion coefficient of this sealing glass. Therefore, by using a stem base or lead pin made of this metal material, a wide range of material combinations become possible in harmonized glass hermetic seals. This allows for the application of harmonized glass hermetic seals to a wide range of applications, resulting in highly reliable glass hermetic seals. Furthermore, cost reductions can be expected through the use of materials such as carbon steel.

[0019] (III) Conventionally, Kovar has been mainly used for the stem base and lead pins of matched-seal glass hermetic seals. However, stem bases and lead pins made of this metal material, which has the characteristics described above, are not merely substitutes for Kovar, but rather completely new and extremely useful metal components that can realize matched-seal glass hermetic seals with an unprecedentedly high level of "seal joint reliability," "heat dissipation performance," and "electrical conductivity." (IV) This metal material can be manufactured relatively easily by reducing the diameter of a material made of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and then reducing the diameter of the material by stretching it into a rod or wire shape. Then, by simply cutting the rod or wire metal material manufactured in this way to a predetermined length, a pin material that will be used as the material for a lead pin can be obtained. Furthermore, by cutting the manufactured rod or wire metal material radially (slicing it into rings) and cutting out a plate material with the axial direction being the thickness direction and the radial direction being the surface direction, a plate material that will be used as the material for a plate-shaped stem base can be obtained. Similarly, by cutting the rod or wire metal material radially (slicing it into rings) and cutting out a plate or block material of a predetermined thickness, hollowing out the center of this plate or block material, and processing it into a cylindrical material with the axial direction being the cylinder axis direction and the radial direction being the cylinder diameter direction, a cylindrical material that will be used as the material for a cylindrical stem base can be obtained.

[0020] This invention is based on the above findings and is summarized as follows. [1] A plate-shaped or cylindrical stem base constituting a harmonized sealing glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the base thickness direction (however, in the case of a plate-shaped stem base, the plate thickness direction; in the case of a cylindrical stem base, the cylindrical axis direction; the same applies hereinafter) in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure in the base horizontal direction (however, in the case of a plate-shaped stem base, the direction parallel to the plate surface; in the case of a cylindrical stem base, the cylindrical diameter direction; the same applies hereinafter) in which fine, flake-like, small, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, and is a stem base for a compatible sealing type glass hermetic seal. [2] In the stem base described in [1] above, the average coefficient of thermal expansion in the base thickness direction from 30°C to 450°C is 12.0 × 10 -6Below / K, the mean horizontal thermal expansion coefficient of the base from 30℃ to 450℃ is 18.0 × 10⁻⁶. -6 A stem base for a harmonized sealing glass hermetic seal, characterized in that it is less than or equal to / K and [average thermal expansion coefficient in the base thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the base horizontal direction from 30°C to 450°C].

[0021] [3] A stem base for a matched sealing type glass hermetic seal, characterized in that the stem base of [1] above has a thermal conductivity of 180 W / m·K or more in the thickness direction of the base. [4] A stem base for a matched sealing type glass hermetic seal, characterized in that the thermal conductivity in the thickness direction of the base is 180 W / m·K or more, as described in [2] above. [5] A stem base for a compatible sealing glass hermetic seal, characterized in that, in any of the stem bases of [1] to [4] above, the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%. [6] A stem base for a conforming sealing type glass hermetic seal, characterized in that any of the stem bases described in [1] to [5] above has a surface treatment coating on at least a portion of its outer surface.

[0022] [7] Lead pins comprising a matched sealing glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretchable material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, as a lead pin for a matching-type sealing glass hermetic seal. [8] In the lead pin described in [7] above, the average axial thermal expansion coefficient from 30°C to 450°C is 12.0 × 10-6 Below / K, the mean radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10⁻⁶. -6 Lead pins for a harmonized sealing type glass hermetic seal, characterized by having a temperature of 0.0 / K or less and [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C].

[0023] [9] In the lead pin described in [7] above, the axial electrical conductivity is 20.0 × 10 6 Lead pins for a matched sealing type glass hermetic seal, characterized by having a density of S / m or greater.

[10] In the lead pin described in [8] above, the axial electrical conductivity is 20.0 × 10 6 Lead pins for a matched sealing type glass hermetic seal, characterized by having a density of S / m or greater.

[11] A lead pin for a matched-seal glass hermetic seal, characterized in that, in any of the lead pins of [7] to

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

[12] A lead pin for a matched sealing type glass hermetic seal, characterized in that any of the lead pins in [7] to

[11] above has a surface treatment coating on at least a part of its outer surface.

[0024]

[13] A hermetic terminal of the matching sealing type, characterized in that it comprises any of the stem bases described in [1] to [6] above.

[14] A hermetic terminal of the matching sealing type, characterized in that it comprises any of the lead pins described in [7] to

[12] above.

[15] A hermetic terminal of the matching sealing type, characterized by comprising a stem base of any of [1] to [6] above and a lead pin of any of [7] to

[12] above.

[16] A semiconductor device equipped with a matched-seal glass hermetic seal, A semiconductor device characterized in that the matched-seal glass hermetic seal comprises any of the stem bases described in [1] to [6] above.

[17] A semiconductor device equipped with a matched-seal glass hermetic seal, A semiconductor device characterized in that the matched-seal glass hermetic seal comprises any of the lead pins described in [7] to

[12] above.

[18] A semiconductor device equipped with a matched-seal glass hermetic seal, A semiconductor device characterized in that the matched-seal glass hermetic seal comprises a stem base of any of [1] to [6] above and lead pins of any of [7] to

[12] above. [Effects of the Invention]

[0025] <Troster Base> The stem base of the present invention allows for the change (adjustment) of the coefficient of thermal expansion in the base thickness direction. Therefore, depending on the coefficient of thermal expansion of the sealing glass used, the coefficient of thermal expansion in the base thickness direction can be brought as close as possible to (and in some cases nearly identical to) that of the sealing glass. This improves the consistency of thermal expansion coefficients with the sealing glass, resulting in high bonding reliability with the sealing glass. Moreover, it has a higher thermal conductivity in the base thickness direction compared to conventional stem bases made of Kovar and other materials. Therefore, the stem base of the present invention can improve the reliability of bonding with sealing glass compared to conventionally used Kovar stem bases, and also has excellent heat dissipation performance in the base thickness direction. For example, it can improve the heat dissipation performance of semiconductor devices and adequately support the increasing power output and performance of semiconductor devices.

[0026] Furthermore, the stem base of the present invention, while being a conforming-seal type glass hermetic seal, can apply compressive stress to the sealing glass (provided the glass hermetic component shape allows for compressive stress to be applied to the sealing glass). Therefore, a conforming-seal type glass hermetic seal incorporating compression sealing can be constructed, increasing the mechanical strength of the seal, and thus further improving the reliability of the bond with the sealing glass can be expected. Furthermore, the stem base of the present invention can change (adjust) the magnitude of the thermal expansion coefficient in the thickness direction of the base according to the thermal expansion coefficient of the lead pins and sealing glass that constitute the harmonized sealing glass hermetic seal. This allows metal materials that have not been used in conventional harmonized sealing glass hermetic seals to be used for the lead pins, enabling a wide range of material combinations in harmonized sealing glass hermetic seals. Therefore, the stem base of the present invention is not merely a replacement for conventionally used Kovar stem bases, but rather a completely new and extremely useful stem base that can realize a matched-seal glass hermetic seal that combines an unprecedentedly high level of "seal joint reliability" and "heat dissipation performance."

[0027] <Lead pin of the present invention> The lead pin of the present invention allows for the change (adjustment) of the axial thermal expansion coefficient, so that, depending on the thermal expansion coefficient of the sealing glass used, the axial thermal expansion coefficient can be brought as close as possible to (and in some cases nearly identical to) that of the sealing glass. By improving the compatibility of thermal expansion coefficients with the sealing glass, high bonding reliability with the sealing glass can be obtained. Moreover, it has a higher axial electrical conductivity compared to conventional lead pins made of Kovar and other materials. Therefore, compared to conventionally used Kovar lead pins, the lead pins of the present invention can improve the reliability of bonding with the sealing glass, reduce the amount of heat generated when energized, and also reduce power consumption in the lead pins.

[0028] Furthermore, the lead pin of the present invention can change (adjust) the magnitude of its axial thermal expansion coefficient according to the thermal expansion coefficients of the stem base and sealing glass constituting the harmonized sealing glass hermetic seal. This allows metal materials, which have not been used in conventional harmonized sealing glass hermetic seals, to be used for the stem base, enabling a wide range of material combinations in harmonized sealing glass hermetic seals. Therefore, the lead pin of the present invention is not merely a replacement for conventionally used Kovar lead pins, but rather a completely new and extremely useful lead pin that can realize a matched-seal type glass hermetic seal that combines an unprecedentedly high level of "bonding reliability of the seal portion" and "electrical conductivity performance."

[0029] <Hermet terminal and semiconductor device of the present invention> A matched-seal type hermetic terminal of the present invention, comprising the stem base and / or lead pins described above, can enjoy the effects of the stem base and / or lead pins of the present invention as described above. Furthermore, a semiconductor device of the present invention that includes a matched-seal glass hermetic seal with the above-mentioned stem base and / or lead pins can enjoy the effects of the stem base and / or lead pins of the present invention described above. [Brief explanation of the drawing]

[0030] [Figure 1] Figure 1(a) is a plan view and Figure 1(b) is a cross-sectional view along line AA in Figure 1(a). [Figure 2] The images show an example of a linear substrate (φ1.2 mm wire made of 50 mass% Cr-Cu composite) that will be used as the material for the stem base and lead pin of the present invention. The images on the left show an SEM image of the material surface, and magnified images of the cross-sectional structure in the stretching direction (axial direction) and the cross-sectional structure in the direction perpendicular to the stretching direction (radial direction) observed with an optical microscope (magnification 120x) on the right and in the center. [Figure 3] These are magnified photographs of the microstructure in the rolling direction and perpendicular to the rolling direction, observed with an optical microscope, of a metallic material (rolled sheet material of 50 mass% Cr-Cu composite) obtained by rolling a 50 mass% Cr-Cu fused body (a Cr sintered body into which Cu is dissolved) into a plate shape using a flat roll. [Figure 4]This diagram schematically shows a cross-section of a plate-shaped stem base, which is one embodiment of the stem base of the present invention. The upper diagram shows the horizontal cross-section of the base (cross-section in the direction of the plate surface), and the lower diagram shows the cross-section in the thickness direction of the base (cross-section in the direction of the plate thickness). [Figure 5(1)] Figures (a) and (b) schematically show cross-sections of cylindrical stem bases, which are other embodiments of the stem base of the present invention. The upper figure shows a cross-section in the thickness direction of the base (cross-section in the direction of the cylinder axis), and the lower figure shows a cross-section in the horizontal direction of the base (cross-section in the diameter direction of the cylinder = cross-section along line BB in the upper figure). [Figure 5(2)] Figures (c) and (d) schematically show cross-sections of plate-shaped stem bases, which are other embodiments of the stem base of the present invention. The upper figure shows a cross-section in the thickness direction of the base (cross-section in the thickness direction of the plate), and the lower figure shows a cross-section in the horizontal direction of the base (cross-section in the direction of the plate surface = cross-section along line BB in the upper figure). [Figure 6] This figure schematically shows a cross-section of one embodiment of the lead pin of the present invention, with the upper figure showing a radial cross-section of the lead pin and the lower figure showing an axial cross-section. [Figure 7] Figure 7(A) is a schematic diagram of a harmonized sealing glass hermetic seal used to examine the bonding reliability when the stem base and lead pin of the present invention are applied to a harmonized sealing glass hermetic seal equipped with an airtight terminal (conceptual diagram showing the dimensions and thermal expansion coefficient of the constituent members, compressive stress within the seal, etc.). Figure 7(A) is a schematic longitudinal section of the entire seal, Figure 7(B) is a schematic plan view of the same, and Figure 7(C) is a schematic plan view of the sealing glass. [Figure 8] Figure 8(A) is a schematic diagram of a harmonized sealing glass hermetic seal used to examine the bonding reliability when the stem base and lead pin of the present invention are applied to a harmonized sealing glass hermetic seal equipped with an airtight terminal (conceptual diagram showing the dimensions and thermal expansion coefficient of the constituent members, compressive stress within the seal, etc.). Figure 8(B) is a schematic longitudinal section of the entire seal, Figure 8(C) is a schematic plan view of the housing (stem base) and sealing glass, and Figure 8(A) is a schematic plan view of the sealing glass and lead pin. [Modes for carrying out the invention]

[0031] Figure 1 schematically shows an example of a matched sealing type glass hermetic seal composed of a stem base and lead pins according to the present invention, where Figure 1(a) is a plan view and Figure 1(b) is a cross-sectional view along line AA in Figure 1(a). This harmonized sealing glass hermetic seal consists of a stem base 1, lead pins 2, sealing glass 3, etc., and is a seal in which the lead pins 2 are hermetically sealed through the insertion hole 4 of the plate-shaped or cylindrical stem base 1 (a through hole drilled in the thickness direction of the plate in the plate-shaped stem base, and a through hole on the inside of the cylinder in the cylindrical stem base) via the sealing glass 3 (sealing material). An oxide film is formed on the surfaces of the stem base 1 and lead pin 2 that are in contact with the sealing glass 3. This oxide film acts as an adhesive to the sealing glass 3, thereby sealing the lead pin. Stem base 1 is sometimes called housing, stem, base, or metal eyelet, and lead pin 2 is sometimes called lead, metal pin, pin, or feedthrough. For illustrative purposes, Figure 1 shows a single-pin structure with one lead pin; however, most matched-seal glass hermetic seals have a multi-pin structure with multiple lead pins.

[0032] <Substrate for the stem base and lead pin of the present invention> The present invention relates to the stem base and lead pins of a matched-seal glass hermetic seal, but first, the metal material constituting these components (hereinafter sometimes referred to as "base material A") will be described. Here, in the above-mentioned substrate A and the stem base and lead pin of the present invention, the [Cr and / or Mo]-Cu composite refers to a Cr-Cu composite having a metallic structure in which the Cr phase is dispersed in a Cu matrix, a Mo-Cu composite having a metallic structure in which the Mo phase is dispersed in a Cu matrix, and a Cr·Mo-Cu composite having a metallic structure in which the Cr phase and Mo phase are dispersed in a Cu matrix.

[0033] Furthermore, in the above-mentioned base material A and the stem base and lead pin of the present invention, the powder metallurgy molded body refers to a molded body obtained by applying the powder metallurgy method, and therefore includes a molded body obtained in step (A) of the manufacturing method described later, for example, (i) obtained through a step (a1) of sintering a molded body (compacted powder) of powder raw materials and a step (a2) of subjecting this sintered body to Cu fusion and / or densification treatment, and (ii) obtained through a step of discharging plasma sintering (SPS sintering) or hot press sintering of powder raw materials. Furthermore, the diameter-reduced and stretched material of the powder metallurgy molded body refers to a material obtained by reducing the diameter and stretching the powder metallurgy molded body as described above by reducing the surface area (diameter-reducing and stretching process).

[0034] Furthermore, in the above-mentioned substrate A and the stem base and lead pin of the present invention, "layered or linear Cr phase and / or Mo phase dispersed in the Cu matrix" includes the case where both "layered Cr phase and / or Mo phase" and "linear Cr phase and / or Mo phase" are dispersed (mixed) in the Cu matrix. Similarly, "flake-like, small-piece-like, or granular Cr phase and / or Mo phase dispersed in the Cu matrix" includes the case where two or more of the following are dispersed (mixed) in the Cu matrix: "flake-like Cr phase and / or Mo phase", "small-piece-like Cr phase and / or Mo phase", and "granular Cr phase and / or Mo phase".

[0035] The above-mentioned substrate A consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or a Mo phase is dispersed in a Cu matrix. This [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded bodies, and when the cross-sectional structure is observed with an optical microscope (for example, at 120x magnification), it has a cross-sectional structure in the stretching direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[0036] The main forms (specific forms) of the above-mentioned base material A include: (1) a rod-shaped or wire-shaped metal material with the stretching direction as the axial direction and the stretching direction perpendicular to the radial direction; (2) a plate-shaped metal material with the stretching direction as the thickness direction and the stretching direction perpendicular to the plate surface direction; and (3) a cylindrical metal material with the stretching direction as the axial direction of the cylinder and the stretching direction perpendicular to the cylinder diameter direction. Of these, the metal material of (1) can be obtained as a material (diameter-reduced stretched material) obtained by reducing the surface area (reducing the diameter) of a powder metallurgy molded body into a rod-shaped or wire-shaped form, while the metal material of (2) can be obtained by cutting the diameter-reduced stretched material obtained by reducing the surface area (reducing the diameter) of a powder metallurgy molded body into a rod-shaped or wire-shaped form in the radial direction (i.e., slicing it into rings), and cutting out a plate material with the axial direction (stretching direction) as the thickness direction and the radial direction (perpendicular to the stretching direction) as the plate surface direction. Furthermore, the metal material of (3) can be obtained in the same manner as in (2) above by cutting the diameter-reduced stretched material radially (i.e., into slices), cutting out a plate or block material of a predetermined thickness, hollowing out the central part of the plate or block material, and processing it into a cylindrical material in which the axial direction (stretching direction) of the diameter-reduced stretched material is the cylindrical axis direction and the radial direction (direction perpendicular to stretching) is the cylindrical diameter direction. Then, (1) above is used as the material for the lead pin of the present invention, and (2) and (3) above are used as the materials for the stem base of the present invention.

[0037] Here, in the description of the base material A and the present invention, "rod-shaped" means "rod-shaped" when referring to "rod-shaped or wire-shaped metal material," "rod-shaped or wire-shaped material," "rod-shaped or wire-shaped base material," or "(to) reduce the diameter and stretch (the material) into a rod-shaped or wire-shaped form," and similarly, "wire-shaped" means "wire-shaped." While there is no strict distinction between rod-shaped materials (rods) and wire-shaped materials (wires), generally speaking, wire-shaped materials refer to those that can be wound up, while rod-shaped materials refer to those that cannot.

[0038] The above-mentioned base material A is obtained by reducing the surface area (reducing the diameter and stretching) of a material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, thereby reducing the diameter and stretching it into a rod or wire shape. As a result, Cr particles and / or Mo particles dispersed in the Cu matrix are stretched into elongated needle-like or rod-like shapes in the stretching direction, creating a Cr phase and / or Mo phase, which has the characteristic cross-sectional structure in the stretching direction and perpendicular to the stretching direction as described above. Furthermore, as will be described later, a [Cr and / or Mo]-Cu composite having such a characteristic cross-sectional structure in the stretching direction and perpendicular to the stretching direction has properties that make it suitable for stem bases and lead pins of matched-seal glass hermetic seals, and such a metallic material ([Cr and / or Mo]-Cu composite) has not been known conventionally.

[0039] Figure 2 shows an example of a linear substrate A (a φ1.2 mm wire made of a 50 mass% Cr-Cu composite), including an SEM image of the material surface (left image), and magnified images of the cross-sectional structure in the stretching direction (axial direction) and perpendicular direction (radial direction) observed with an optical microscope (magnification 120x) (right image) (center image). In these cross-sectional structures in the stretching direction and perpendicular direction (axial and radial directions), the darker areas are the Cr phase dispersed in the Cu matrix (lighter areas). The manufacturing conditions for this substrate A were as follows: a prismatic material for surface reduction (thickness 9 mm) was subjected to surface reduction (diameter reduction stretching) by swaging and subsequent combined roll rolling, and then further surface reduction (diameter reduction stretching) by roller die drawing (CRD) to an outer diameter of φ1.2 mm.

[0040] From the pin material cut from this base material A to the length of a lead pin, a lead pin of the present invention is obtained in which the stretching direction of base material A is the axial direction and the direction perpendicular to the stretching direction is the radial direction. Furthermore, from the plate material cut from this base material A (however, when obtaining a stem base, a base material thicker than the above outer diameter is usually used) in the radial direction (by slicing it into rings), a plate-shaped stem base of the present invention is obtained in which the stretching direction of base material A is the thickness direction and the direction perpendicular to the stretching direction is the surface direction. Furthermore, from the cylindrical material obtained by cutting a plate material or block material from the same base material A in the radial direction (by slicing it into rings), hollowing out the central part, and processing it into a cylindrical shape, a cylindrical stem base of the present invention is obtained in which the stretching direction of base material A is the axis direction of the cylinder and the direction perpendicular to the stretching direction is the diameter direction of the cylinder.

[0041] As described above, this base material A is made by reducing the surface area (reducing the diameter and stretching) of a Cr-Cu composite (powder metallurgy molded body) obtained by powder metallurgy, and stretching it into a rod or wire shape. As a result, the Cr particles dispersed in the Cu matrix of the above material (powder metallurgy molded body) are stretched into a long, thin shape like a needle or rod (not a "flat" shape like the rolled plate material in Figure 3, which will be described later), resulting in the cross-sectional structure shown in Figure 2. In other words, the cross-sectional structure in the stretching direction (axial direction) observed with an optical microscope is a cross-section of the needle-shaped or rod-shaped Cr phase, resulting in layered or linear Cr phases dispersed within the Cu matrix. These layered (or "strip-shaped") or linear Cr phases exist in a long, extended state along the stretching direction (axial direction) of the material, and typically consist of a mixture of layered structures with a certain width and thin linear structures. Of these, the layered structures with a certain width are thought to be Cr phases formed by the stretching and fusion of multiple adjacent Cr particles, for the reasons described below. In the stretching direction (axial direction) cross-sectional structure of Figure 2, the Cr phase consists of layered structures with a certain width and thin linear structures, both dispersed within the Cu matrix in a state extended along the stretching direction (axial direction) of the material.

[0042] On the other hand, the cross-sectional structure observed with an optical microscope in the direction perpendicular to the stretching direction (radial direction) is such that the needle-shaped or rod-shaped Cr phase is cross-sectioned in the direction perpendicular to the stretching direction, resulting in a dispersion of flaky, small-piece, or granular Cr phase within the Cu matrix. Typically, the Cr phase in this cross-sectional structure is a mixture of flaky, small-piece, and granular particles. The reason why the Cr phase in the cross-sectional structure perpendicular to the stretching direction appears flaky or small-piece is thought to be that when the material (powder metallurgy molded body) is stretched to a reduced diameter, the Cr particles are elongated into a needle-shaped or rod-shaped form, causing density variations in the distribution of the Cr phase perpendicular to the stretching direction, resulting in some Cr phase particles coming into close proximity, contact, or accreting together. In the cross-sectional structure perpendicular to the stretching direction (radial direction) shown in Figure 2, fine Cr phase (flaky, small-piece, or granular Cr phase) is dispersed relatively uniformly within the Cu matrix. These Cr phases, which appear as flaky, small, or granular pieces, are, as mentioned above, cross-sections perpendicular to the stretching direction (radial direction) of the Cr phase that has been elongated into a needle-like or rod-like shape. Figure 2 shows the cross-sectional structure in the stretching direction and perpendicular to the stretching direction (axial and radial directions) of a linear metallic material made of a Cr-Cu composite, which is one of the substrates A (φ1.2 mm wire made of 50 mass% Cr-Cu composite). Substrates A made of Mo-Cu composite and Cr·Mo-Cu composite will have similar cross-sectional structures in the stretching direction and perpendicular to the stretching direction (axial and radial directions).

[0043] For comparison, Figure 3 shows the microstructure in the rolling direction and perpendicular to the rolling direction as observed with an optical microscope for a 50 mass%Cr-Cu composite sheet roll, i.e., a 50 mass%Cr-Cu fused body (a Cr sintered body into which Cu is dissolved) rolled into a sheet using flat rolls. In the case of this Cr-Cu composite sheet roll, there is no significant difference between the microstructure in the rolling direction and perpendicular to the rolling direction. In both directions, with a reduction ratio of 75%, the Cr phase is dispersed in the Cu matrix in a pseudo-network-like manner, while with a reduction ratio of 98%, the Cr phase, stretched in one direction, is dispersed in the Cu matrix in a flattened (pseudo-fibrous) manner. Comparing this to Figure 3, it can be seen that base material A in Figure 2 has a very distinctive microstructure in the stretching direction and perpendicular to the stretching direction (axial and radial directions). In particular, regarding the cross-sectional structure perpendicular to the stretching direction, the rolled plate material in Figure 3 has a form in which the Cr phase is thinly stretched in a flattened (pseudo-fibrous) shape, whereas the base material A in Figure 2 has a form in which the Cr phase is dispersed in the form of fine flakes, small pieces, or granules (cross-sectional shape perpendicular to the stretching direction of the Cr phase which is stretched into a long, thin, needle-like or rod-like shape in the stretching direction), exhibiting a completely different form.

[0044] Here, the Cr-Cu composite sheet rolled material shown in Figure 3 was developed for use as a heat sink for bonding semiconductors and ceramics with low thermal expansion coefficients between the sheet surface. Due to the cross-sectional structure described above, the thermal expansion coefficient in the sheet surface direction (rolling direction and direction perpendicular to rolling) is small, while the thermal expansion coefficient in the sheet thickness direction is large. Therefore, if a shaft is cut from this sheet rolled material with the rolling direction as the axial direction to form a lead pin, the thermal expansion coefficient in the pin radial direction will be anisotropic, and the difference in thermal expansion between the lead pin and the sealing glass will be large in one direction of the cross-section in the pin radial direction, making it impossible to form a harmonized sealing type glass hermetic seal. Furthermore, even if a harmonized sealing type glass hermetic seal could be formed, sufficient bonding reliability could not be obtained, such as cracks occurring in the sealing glass. Furthermore, when the above-mentioned rolled plate material is used as the stem base, the thermal expansion coefficient in the plate surface direction is small. Even if the thermal expansion coefficient in the plate surface direction can be matched to that of the sealing glass, the thermal expansion coefficient in the plate thickness direction is large. As a result, the difference in thermal expansion with the sealing glass in the plate thickness direction becomes large, making it impossible to construct a harmonized sealing glass hermetic seal. Moreover, even if a harmonized sealing glass hermetic seal could be constructed, the interfacial shear stress with the sealing glass in the plate thickness direction would be high, resulting in insufficient bonding reliability. In addition, the Cr phase, which has a lower thermal conductivity than the Cu phase and is flattened by rolling, obstructs heat flow in the plate thickness direction. Therefore, the thermal conductivity in the plate thickness direction is also low, and there are problems with heat dissipation. In contrast, base material A possesses unique properties (characteristics) that are completely different from conventionally known metallic materials, and does not suffer from any of the problems seen in the rolled Cr-Cu composite sheet (Figure 3) described above. These characteristics will be described in detail later as the characteristics of the stem base and lead pin of the present invention.

[0045] <Troster Base> ●Basic configuration of the stem base of the present invention The stem base of the present invention is a plate-shaped or cylindrical stem base constituting a conforming sealing type glass hermetic seal, wherein the stretching direction of the above-mentioned base material A is the base thickness direction (however, in the case of a plate-shaped stem base, the plate thickness direction, and in the case of a cylindrical stem base, the cylindrical axis direction; the same applies hereinafter), and the stretching direction perpendicular to the stretching direction is the base horizontal direction (however, in the case of a plate-shaped stem base, the direction parallel to the plate surface, and in the case of a cylindrical stem base, the cylindrical diameter direction; the same applies hereinafter). That is, this stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope, it is characterized by having a cross-sectional structure in the base thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure in the base horizontal direction in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix.

[0046] As described later, the stem base of the present invention may have a surface treatment coating (mainly a plating coating) on ​​its outer surface (or at least a part of its outer surface). However, in the following description, "stem base" mainly refers to the base body excluding such a surface treatment coating. Here, in the stem base of the present invention, the technical meanings of "[Cr and / or Mo]-Cu composite," "powder metallurgy molded body," "diameter-reduced and drawn material for powder metallurgy molded body," "layered or linear Cr phase and / or Mo phase dispersed in a Cu matrix," and "flake-like, small-piece-like, or granular Cr phase and / or Mo phase dispersed in a Cu matrix" are as explained above.

[0047] Figure 4 schematically shows a cross-section of a plate-shaped stem base, which is one embodiment of the stem base of the present invention. The upper part of Figure 4 shows the horizontal cross-section of the base, i.e., the cross-section parallel to the plate surface of the stem base (cross-section in the direction of the plate surface), and the lower part shows the cross-section in the thickness direction of the base, i.e., the cross-section in the direction of the plate thickness. These cross-sectional views schematically represent the cross-section of the Cr phase and / or Mo phase generated by stretching Cr particles and / or Mo particles dispersed in the Cu matrix into a needle-like or rod-like shape in the stretching direction. The stem base of this embodiment has two insertion holes 4 formed (drilled) through which lead pins are inserted and sealed.

[0048] In the cross-section in the thickness direction of Figure 4 (lower figure), the short linear elements represent "layered or linear Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph on the right side of Figure 2. Also, in the cross-section in the surface direction of Figure 4 (upper figure), the dot-like elements represent "flake-like, small-piece-like, or granular Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph in the center of Figure 2. This stem base in Figure 4 is composed of a plate material (plate-like body) in which the stretching direction of the aforementioned base material A is the thickness direction and the direction perpendicular to the stretching direction is the surface direction. Typically, the rod-shaped or linear base material A is cut radially to an appropriate thickness (i.e., the material is sliced ​​into rings) to cut out the above-mentioned plate material, which is used as the material for the stem base.

[0049] Figures 5(1) and 5(2), and so on, (a) to (d) schematically show other embodiments of the stem base of the present invention, where the upper figure shows a cross-section in the thickness direction of the base, and the lower figure shows a cross-section in the horizontal direction of the base (a cross-section along the BB line in the upper figure). For reference, lead pins sealed to the stem base are shown by dashed lines. Figures 5(a) and 5(b) show cylindrical stem bases, with the upper figure showing a cross-section in the axial direction of the cylinder (cross-section in the thickness direction of the base) and the lower figure showing a cross-section in the radial direction of the cylinder (cross-section in the horizontal direction of the base). In the stem base of Figure 5(b), a flange portion 11 is provided on the outer circumference of the upper end of the cylindrical body 10. In this cylindrical stem base of Figures 5(a) and 5(b), the through hole on the inside of the cylinder constitutes an insertion hole 4 through which a lead pin is inserted and sealed. On the other hand, Figures 5(c) and (d) show plate-shaped stem bases, with the upper figure showing a cross-section in the thickness direction of the plate (base thickness direction cross-section), and the lower figure showing a cross-section parallel to the plate surface (base horizontal direction cross-section). In the stem base of Figure 5(c), a flange portion 12 is provided on the outer circumference of the lower end of the plate-shaped body 10. In the stem base of Figure 5(d), a skirt portion 13 is provided on the outer circumference of the plate-shaped body 10, and a flange portion 12 is provided on the outer circumference of the lower end of this skirt portion 13, and the overall cross-section (vertical cross-section) is configured to be cap-shaped or hat-shaped. The stem bases of Figures 5(c) and (d) have two insertion holes 4 formed (drilled) through which lead pins are inserted and sealed.

[0050] Similar to the embodiment in Figure 4, in the base thickness-direction cross-sections (upper figure) of Figures 5(a) to (d), the short linear elements represent "layered or linear Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph on the right side of Figure 2. Furthermore, in the base horizontal-direction cross-sections (lower figure) of Figures 5(a) to (d), the dot-like elements represent "flake-like, small-piece-like, or granular Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph in the center of Figure 2.

[0051] Here, the plate-shaped stem bases in Figures 5(c) and (d) are composed of a plate material (plate-like body) in which the stretching direction of the base material A described above is the plate thickness direction and the direction perpendicular to the stretching direction is the plate surface direction, similar to the stem base in Figure 4. Typically, a rod-shaped or wire-shaped base material A is cut to an appropriate thickness in the radial direction (i.e., sliced ​​into rounds) to cut out plate material, which is used as the material for the stem base. The flange portion 12 and the skirt portion 13 are formed by processing the plate material, such as cutting it in the thickness direction. On the other hand, the cylindrical stem bases in Figures 5(a) and (b) are composed of a cylindrical material in which the stretching direction of the base material A described above is the cylindrical axis direction and the direction perpendicular to the stretching direction is the cylindrical diameter direction. Typically, a rod-shaped or wire-shaped base material A is cut to an appropriate thickness in the radial direction (i.e., sliced ​​into rounds) to cut out plate material or block material, and the central part of this plate material or block material is hollowed out to form a cylindrical material, which is used as the material for the stem base. The flange portion 11 is formed by processing the cylindrical material, such as cutting it in the cylindrical axis direction. Furthermore, the plate-shaped or cylindrical stem base of the present invention can take various forms other than those shown in Figures 5(a) to (d), and is therefore not limited to the embodiments shown in Figures 4 and 5.

[0052] As explained earlier, the metal material constituting the stem base of the present invention is obtained by reducing the surface area (reducing the diameter of the material) of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and then reducing the diameter of the material by stretching it into a rod or wire shape. The stretching direction is the thickness direction and the direction perpendicular to the stretching is the surface direction, or the stretching direction is the axis of the cylinder and the direction perpendicular to the stretching is the diameter direction. For this reason, the stem base of the present invention generates a Cr phase and / or Mo phase in which Cr particles and / or Mo particles dispersed in the Cu matrix are stretched into an elongated needle-like or rod-like shape in the base thickness direction (plate thickness direction or cylinder axis direction), resulting in the characteristic cross-sectional structure in the base thickness direction and base horizontal direction described above. Furthermore, [Cr and / or Mo]-Cu composites having such characteristic base thickness-direction and base horizontal cross-sectional structures possess unique properties, particularly those suitable for the stem base of a compatible sealing type glass hermetic seal, and such metallic materials ([Cr and / or Mo]-Cu composites) have not been known before.

[0053] Matching-type glass hermetic seals typically have a multi-pin structure, and the planar shape of the stem base can vary, such as circular, oval, or rectangular. Therefore, the stem base of the present invention can also have such a variety of planar shapes. As described above, the plate-shaped body (plate material) that serves as the material for the plate-shaped stem base of the present invention can be obtained by cutting a diameter-reduced and stretched material, obtained by reducing the surface area (reducing the diameter) of a powder metallurgy molded body into a rod-shaped or linear shape, in the radial direction (i.e., into slices), and cutting out a plate material in which the axial direction (stretching direction) of the diameter-reduced and stretched material is the plate thickness direction and the radial direction (direction perpendicular to stretching) is the plate surface direction. Furthermore, the cylindrical body (cylindrical material) that serves as the material for the cylindrical stem base of the present invention can be obtained by cutting a diameter-reduced and stretched material, obtained by reducing the surface area (reducing the diameter) of a powder metallurgy molded body into a rod-shaped or linear shape, in the radial direction (i.e., into slices), cutting out a plate material or block material, and hollowing out the central part of the plate material or block material, thereby processing it into a cylindrical material in which the axial direction (stretching direction) of the diameter-reduced and stretched material is the cylindrical axis direction and the radial direction (direction perpendicular to stretching) is the cylindrical diameter direction. In the manufacturing process of plate-like or cylindrical bodies as described above, if the surface reduction (diameter reduction and stretching) is performed by hot extrusion, it is possible to obtain a rod-shaped material with a cross-sectional shape other than circular (for example, oval). By cutting this rod-shaped material radially, it is possible to obtain plate-like or cylindrical bodies that are close in shape to the stem base itself as described above.

[0054] ● Characteristics of the stem base of the present invention As mentioned earlier, the stem base constituting a harmonized glass hermetic seal must have a thermal expansion coefficient in the thickness direction of the base that is as close as possible to the thermal expansion coefficient of the sealing glass, provide high bonding reliability that can maintain a proper bonding state with the sealing glass for a long period of time, and have a sufficiently high thermal conductivity in the thickness direction of the base. The stem base of the present invention has a unique property (characteristic) that differs from the stem base of conventional harmonically sealed glass hermetic seals because it has the above-described cross-sectional structure in the base thickness direction and the base horizontal direction. Specifically, the stem base of the present invention has a base thickness direction thermal expansion coefficient < base horizontal direction thermal expansion coefficient, meaning the base thickness direction thermal expansion coefficient is relatively small. As shown in the examples described later, the materials of the present invention all have a stretch direction (stem base thickness direction) thermal expansion coefficient < stretch direction perpendicular to stretch (stem base horizontal direction) thermal expansion coefficient, meaning the stretch direction (stem base thickness direction) thermal expansion coefficient is relatively low. Furthermore, the stem base of the present invention is a diameter-reduced stretched material of a powder metallurgy molded body, and because it has the above-described cross-sectional structure in the stretch direction (base thickness direction) and the stretch direction perpendicular to stretch (base horizontal direction), its base horizontal direction thermal expansion coefficient is the same in any direction of the base horizontal, and the base horizontal direction thermal expansion coefficient is isotropic.

[0055] Furthermore, the stem base of the present invention possesses the following characteristics, which are particularly useful and distinctive for a stem base of a matched-seal glass hermetic seal: (i) and (ii). (i) The magnitude of the thermal expansion coefficient in the base thickness direction changes depending on the blending ratio (content) of Cr and / or Mo in the [Cr and Mo]-Cu composite and the reduction ratio during the reduction of diameter of the material due to the reduction of diameter (reduced diameter stretching process). By selecting these blending ratios and reduction ratios, the magnitude of the thermal expansion coefficient in the base thickness direction can be changed (adjusted). For this reason, depending on the thermal expansion coefficient of the sealing glass used, the thermal expansion coefficient in the base thickness direction can be made as close as possible to the thermal expansion coefficient of the sealing glass (in some cases, they can be made to be almost identical), and by improving the consistency of thermal expansion coefficients with the sealing glass, high bonding reliability with the sealing glass can be obtained. (ii) Those with high thermal conductivity in the base thickness direction, and those with optimized properties, have significantly higher thermal conductivity in the base thickness direction compared to conventional stem bases, which mainly use Kovar.

[0056] To specifically explain the characteristics of (i) above, the stem base of the present invention can have its thermal expansion coefficient in the base thickness direction reduced as the proportion of Cr and / or Mo is increased, provided that the reduction ratio of the material during diameter reduction and stretching is the same, and as the reduction ratio of Cr and / or Mo is increased up to approximately 97% during diameter reduction and stretching, provided that the proportion of Cr and / or Mo is the same. Therefore, the thermal expansion coefficient in the base thickness direction of the stem base can be brought as close as possible to (and in some cases nearly identical to) the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the bond between the stem base and the sealing glass in a harmonized sealing glass hermetic seal.

[0057] To illustrate this using the examples described later, for instance, in the examples, materials No. 5, 10, 15, and 20 of the present invention are made of Cr-Cu composites with a reduction ratio of 90.3% and different Cr content, and the axial thermal expansion coefficient (thermal expansion coefficient in the base thickness direction for stem bases; the same applies hereinafter) decreases as the Cr content increases. Also, materials No. 24 and 29 of the present invention are made of Mo-Cu composites with a reduction ratio of 97.6% and different Mo content, and materials No. 37 and 39 of the present invention are made of Mo-Cu composites with a reduction ratio of 80% and different Mo content, but in all cases, the axial thermal expansion coefficient decreases as the Mo content increases. On the other hand, for example, the materials of the present invention No. 7 to 12 consist of Cr-Cu composites with a Cr content of 45 mass% and different reduction ratios, and the materials of the present invention No. 26 to 29 consist of Mo-Cu composites with a Mo content of 40 mass% and different reduction ratios. In both cases, the axial thermal expansion coefficient decreases as the reduction ratio increases. Therefore, the thermal expansion coefficient in the base thickness direction of the stem base can be brought as close as possible to the thermal expansion coefficient of the sealing glass, and the reliability of the bond between the stem base and the sealing glass in a harmonized sealing glass hermetic seal can be maximized. In particular, as will be described later, it is preferable that the value of τ1 / P1 (=[axial compressive shear stress τ1 acting from the stem base to the sealing glass interface] / [radial compressive stress P1 from the stem base to the sealing glass]) be as small as possible, as this increases the reliability of the bond between the stem base and the sealing glass. It is possible to adjust the thermal expansion coefficient of the stem base in the base thickness direction (to approach the thermal expansion coefficient of the sealing glass) so that such a τ1 / P1 is achieved.

[0058] Furthermore, regarding the characteristics of (ii) described above, the example described later shows that the material of the present invention has a significantly higher thermal conductivity in the stretching direction (base thickness direction of the stem base) compared to Kovar (comparative example No. 31), which is widely used in the stem base of conventional matched-seal glass hermetic seals. Furthermore, regarding the thermal conductivity in the thickness direction of the base, the present invention's stem base exhibits a change in thermal conductivity in the thickness direction depending on the reduction ratio during diameter reduction stretching. If the blending ratio of Cr and / or Mo is the same, the thermal conductivity in the thickness direction of the base increases as the reduction ratio increases up to approximately 97% during diameter reduction stretching. For example, looking at the present invention materials No. 7 to 12 (Cr blending ratio 45 mass%) and No. 26 to 29 (Mo blending ratio 40 mass%) in the examples mentioned above, the axial thermal conductivity (thermal conductivity in the thickness direction of the base in the case of the stem base) increases as the reduction ratio increases. Therefore, by changing (selecting) the reduction ratio, it is possible to appropriately adjust not only the thermal expansion coefficient in the thickness direction of the base as described above, but also the thermal conductivity in the thickness direction of the stem base according to the applicable equipment. As is clear from the examples, the thermal conductivity in the thickness direction of the base also changes depending on the component composition of the stem base (blending ratio of Cr and / or Mo), and the lower the blending ratio of Cr and / or Mo, the higher the thermal conductivity in the thickness direction of the base.

[0059] Furthermore, the stem base of the present invention has a thermal expansion coefficient in the thickness direction of the base < thermal expansion coefficient in the horizontal direction of the base, and the thermal expansion coefficient in the horizontal direction of the base is isotropic. When the thermal expansion coefficient in the thickness direction of the base is matched to the thermal expansion coefficient of the sealing glass, the thermal expansion coefficient in the horizontal direction of the base becomes greater than the thermal expansion coefficient of the sealing glass. Therefore, even though it is a harmonized sealing type glass hermetic seal, compressive stress can be applied to the sealing glass (however, it is naturally a condition that the glass hermetic component shape allows compressive stress to be applied to the sealing glass). As a result, a harmonized sealing type glass hermetic seal that takes compression sealing into account can be constructed, and the mechanical strength of the seal can be increased, so a further improvement in the reliability of the bond with the sealing glass can be expected. This effect is obtained by the characteristics of the stem base of the present invention, as described above, that "thermal expansion coefficient in the thickness direction of the base < thermal expansion coefficient in the horizontal direction of the base, and the thermal expansion coefficient in the horizontal direction of the base is isotropic."

[0060] As described above, the stem base of the present invention allows for the change (adjustment) of the coefficient of thermal expansion in the base thickness direction. Therefore, depending on the coefficient of thermal expansion of the sealing glass used, the coefficient of thermal expansion in the base thickness direction can be brought as close as possible to (and in some cases nearly identical to) that of the sealing glass. By improving the consistency of thermal expansion coefficients with the sealing glass, high bonding reliability with the sealing glass can be obtained. For this reason, compared to conventional stem bases of matched sealing glass hermetic seals that generally use Kovar, the consistency of thermal expansion coefficients with the sealing glass is improved to an equivalent or greater degree, further enhancing the reliability of the airtightness of matched sealing glass hermetic seals. Moreover, compared to conventional stem bases that use Kovar, it has a high thermal conductivity in the base thickness direction and excellent heat dissipation performance in the base thickness direction. For example, it can improve the heat dissipation performance of semiconductor devices and adequately support the increased power output and performance of semiconductor devices. Furthermore, depending on the shape of the stem base, it is possible to apply compressive stress to the sealing glass even in a matched-seal glass hermetic seal. This allows for the construction of a matched-seal glass hermetic seal that incorporates compression sealing, thereby increasing the mechanical strength of the seal and further improving the reliability of the bond with the sealing glass.

[0061] Furthermore, as described above, since the stem base can change (adjust) the magnitude of its thermal expansion coefficient in the base thickness direction, when using other metal materials for the lead pins in a matched-seal glass hermetic seal equipped with the stem base of the present invention, it is possible to use metal materials (such as Ni-Fe material) that have not been conventionally used in matched-seal glass hermetic seals. For example, when using Ni-Fe material for the lead pins, a sealing glass with a thermal expansion coefficient corresponding to that of Ni-Fe material can be used, and the thermal expansion coefficient of the stem base in the base thickness direction of the present invention can be matched to the thermal expansion coefficient of this sealing glass. Therefore, by using the stem base of the present invention, a wide range of material combinations become possible in matched-seal glass hermetic seals. For this reason, it is expected that matched-seal glass hermetic seals can be applied to a wide range of applications as highly reliable glass hermetic seals. Therefore, the stem base of the present invention is not merely a replacement for the Kovar stem base that has been widely used in conventionally matched-seal glass hermetic seals, but rather a completely new and extremely useful stem base that can realize a matched-seal glass hermetic seal that combines an unprecedentedly high level of "bonding reliability of the seal portion" and "heat dissipation performance."

[0062] Here, regarding the thermal properties of the metal material constituting the stem base of the present invention, as described above, the reason why the thermal expansion coefficient in the stretching direction (the thickness direction of the stem base) is smaller than the thermal expansion coefficient in the direction perpendicular to stretching (the horizontal direction of the stem base) is thought to be because the expansion of Cu in the stretching direction is suppressed by the shear stress at the interface between the Cr phase and / or Mo phase, which has been stretched into a needle-like or rod-like shape by the diameter reduction stretching process, and Cu. However, since the range affected by the shear stress of one Cr phase and / or Mo phase in the cross section perpendicular to stretching is limited, the higher the density of the Cr phase and / or Mo phase in the cross section perpendicular to stretching, that is, the higher the blending ratio (content) of Cr and / or Mo, the smaller the thermal expansion coefficient in the stretching direction tends to be. Furthermore, the longer the stretched length of the Cr phase and / or Mo phase in the stretching direction, the greater the shear stress. As will be described later, when manufacturing the stem base (a rod-shaped or wire-shaped metal material before cutting out plate material, etc.) of the present invention, a large reduction ratio increases the stretched length of the Cr phase and / or Mo phase in the stretching direction, and the coefficient of thermal expansion in the stretching direction decreases. In other words, the larger the reduction ratio, the smaller the coefficient of thermal expansion in the stretching direction tends to be. Note that the coefficient of thermal expansion perpendicular to the stretching direction tends to increase with a larger reduction ratio. This is because a larger reduction ratio results in a smaller diameter of the Cr phase and / or Mo phase in the direction perpendicular to the stretching direction, and the restraining force of Cu in the direction perpendicular to the stretching direction decreases. From the above, it can be seen that the coefficient of thermal expansion in the stretching direction (base thickness direction of the stem base) and the direction perpendicular to the stretching direction (base horizontal direction of the stem base) can be adjusted by selecting the blending ratio (content) of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter. Furthermore, the reason why the thermal conductivity in the stretching direction (the base thickness direction of the stem base) increases as the reduction ratio increases is thought to be because, as the reduction ratio increases, the Cu phase is also stretched in the stretching direction by the Cr phase and / or Mo phase that are stretched in the stretching direction, and the heat flow preferentially flows in the stretching direction.

[0063] Here, the characteristics of the stem base of the present invention are determined as follows. The thermal expansion coefficients in the base thickness direction and the base horizontal direction are measured using a push-rod type displacement detection method. The average thermal expansion coefficients in the base thickness direction and the base horizontal direction from 30°C to 450°C are calculated by measuring the thermal expansion coefficients in the base thickness direction and the base horizontal direction, respectively, using the push-rod type displacement detection method, determining the difference in elongation between 30°C and 450°C, and dividing that value by the temperature difference of 420°C (= 450°C - 30°C). Furthermore, the thermal conductivity in the thickness direction of the base (thermal conductivity at room temperature) cannot be measured directly due to the small diameter of the material, so it is calculated from the electrical conductivity based on the Wiedemann-Franz law. That is, the ratio of the thermal conductivity to the electrical conductivity of a metal is equal to the product of the absolute temperature T and a constant L (Lorentz constant) that does not depend on the type of metal (thermal conductivity κ / electrical conductivity σ = LT L: 2.44 × 10⁻¹⁰). -8 WΩK -2 Therefore, the thermal conductivity in the base thickness direction can be calculated from the electrical conductivity in the base thickness direction. The electrical conductivity in the base thickness direction is measured using a commercially available electrical resistance measuring device with the DC four-terminal method (measurement temperature: room temperature, atmosphere: air).

[0064] ● Preferred conditions (configuration and characteristics) for the stem base of the present invention As described above, the stem base of the present invention has the following characteristics: (1) the thermal expansion coefficient in the thickness direction of the base is less than the thermal expansion coefficient in the horizontal direction of the base, the thermal expansion coefficient in the thickness direction of the base is relatively small, and the thermal expansion coefficient in the horizontal direction of the base is isotropic; (2) the magnitude of the thermal expansion coefficient in the thickness direction of the base can be changed by selecting the blending ratio of Cr and / or Mo and the reduction ratio during diameter reduction stretching; and (3) the thermal conductivity in the thickness direction of the base is sufficiently high. However, as the optimal thermal properties, the average thermal expansion coefficient in the thickness direction of the base from 30°C to 450°C is 12.0 × 10⁻⁶.-6 Below / K, the base horizontal direction average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 Below / K, and it is preferable that [the base thickness direction average thermal expansion coefficient from 30°C to 450°C] < [the base horizontal direction average thermal expansion coefficient from 30°C to 450°C]. Also, in order to sufficiently obtain the effect that the stem base compresses the sealing glass and the lead pins in the base horizontal direction, it is preferable that the above-mentioned base horizontal direction thermal expansion coefficient is relatively large. From this perspective, the base horizontal direction average thermal expansion coefficient from 30°C to 450°C is 13.0×10 -6 It is preferably above / K.

[0065] If the base thickness direction average thermal expansion coefficient from 30°C to 450°C is 12.0×10 -6 Below / K, it is particularly effective for obtaining the above-mentioned effect. That is, if the base thickness direction average thermal expansion coefficient is within the above range, it is close to the thermal expansion coefficient of the sealing glass, so the bonding reliability with the sealing glass is easily obtained, which is preferable. On the other hand, regarding the lower limit of the base thickness direction average thermal expansion coefficient from 30°C to 450°C, there are no particularly preferable conditions, nor is it particularly limited. However, in relation to the composition of the material, the area reduction rate, etc., generally, about 7.0×10 -6 / K is the lower limit. Also, according to the thermal expansion coefficient of the sealing glass used, the base thickness direction thermal expansion coefficient can be appropriately adjusted (selected) within the above range. As described above, the base thickness direction average thermal expansion coefficient can be adjusted by changing the component composition (mixing ratio of Cr or / and Mo) of the metal material and the area reduction rate during the reduction and stretching of the material. Also, regarding the point that the base horizontal direction thermal expansion coefficient > the base thickness direction thermal expansion coefficient, which is a characteristic of the thermal properties of the stem base of the present invention, in the following examples (invention examples), in all cases, the difference between [the average thermal expansion coefficient in the stretching direction (base thickness direction) from 30°C to 450°C] and [the average thermal expansion coefficient in the direction perpendicular to the stretching (base horizontal direction) from 30°C to 450°C] is 2.0×10 -6 It is above / K.

[0066] The reason for using the average thermal expansion coefficient from 30°C to 450°C for both the base thickness direction and the base horizontal direction is as follows: While sealing glass is typically used with a glass transition temperature (Tg) in the range of 410-560°C, the volume of sealing glass is determined at a temperature around the glass transition temperature -30°C. Therefore, sealing glass with a glass transition temperature of 410-560°C will have its volume determined at a temperature of approximately 380-530°C. However, the average thermal expansion coefficient within this temperature range does not change significantly with temperature, so 450°C, which is approximately the midpoint between 380-530°C, is used as a representative temperature, resulting in the "average thermal expansion coefficient from 30°C to 450°C."

[0067] Furthermore, the stem base of the present invention preferably has a thermal conductivity of 180 W / m·K or higher in the thickness direction of the base as an optimal characteristic. A thermal conductivity of 180 W / m·K or higher in the thickness direction of the base is particularly effective in obtaining the effects described above. High thermal conductivity in the base thickness direction is a particularly useful characteristic for stem bases. A base thickness direction thermal conductivity of 180 W / m·K or higher is significantly higher than that of Kovar and other materials widely used in conventionally matched-seal glass hermetic seal stem bases, resulting in particularly high heat dissipation characteristics in the stem base thickness direction. In other words, as shown in the examples described later, the thermal conductivity in the extension direction (axial direction, thickness direction of the stem base) of Kovar (comparative example No. 31), which is widely used in conventional stem bases, is 17 W / m·K, and the thermal conductivity of carbon steel is about 40-60 W / m·K. In contrast, the thermal conductivity of the material of the present invention in the extension direction (axial direction, base thickness direction of the stem base) is several times higher, demonstrating that significantly higher thermal conductivity in the extension direction (axial direction, base thickness direction of the stem base) is obtained. As mentioned earlier, the thermal conductivity of this stem base in the base thickness direction can also be adjusted by selecting the component composition of the metal material (the proportion of Cr and / or Mo) and the reduction ratio when the material is stretched to reduce its diameter.

[0068] The stem base of the present invention has the characteristic cross-sectional structure in the base thickness direction (stretching direction) and the base horizontal direction (perpendicular to stretching direction) as shown in Figure 2, and therefore has the unique properties (characteristics) described above. Therefore, the content (mixing ratio) of Cr and / or Mo in the [Cr and Mo]-Cu composite constituting the stem base of the present invention is not particularly limited, but a total Cr and / or Mo content of 35 to 60 mass% is particularly effective in obtaining the thermal properties described above. This is because if the total Cr and / or Mo content decreases, the restraining force of Cu by the Cr phase and / or Mo phase decreases, making it difficult to reduce the thermal expansion coefficient of the material, especially the thermal expansion coefficient in the base thickness direction. On the other hand, if the total Cr and / or Mo content increases, the processability of the material decreases, making it difficult to perform surface reduction processing (diameter reduction stretching) into a rod or wire shape, and it becomes difficult to increase the thermal conductivity in the base thickness direction.

[0069] In the [Cr and / or Mo]-Cu composite constituting the stem base of the present invention, when comparing Cr (Cr phase) and Mo (Mo phase) blended with Cu, there is a tendency that (i) Cr improves the processability (rollability, etc.) of the material compared to Mo, (ii) Mo makes it easier to achieve a higher thermal conductivity in the base thickness direction than Cr, and (iii) Mo makes it easier to achieve a lower coefficient of thermal expansion in the base thickness direction than Cr (the tendencies of (ii) and (iii) above can also be confirmed in the examples described later). Therefore, for example, in a Cr·Mo-Cu composite, the thermal properties can be balanced by adjusting the content and ratio of Cr and Mo according to the required thermal properties, thereby obtaining optimal thermal properties.

[0070] The stem base of the present invention may have a surface treatment coating (mainly a plating coating) on ​​its outer surface (or at least a portion of its outer surface). In matched-seal glass hermetic seals, a surface treatment film (mainly a plating film) is typically formed on the outer surface (or at least a portion of the outer surface) of the stem base. Examples of this surface treatment film include a plating film formed after the assembly of the stem base and lead pin (a), and a plating film formed as needed before the assembly of the stem base and lead pin (b), as shown below.

[0071] In the manufacture of matched-seal glass hermetic seals, the stem base and lead pins are typically oxidized before assembly to form an oxide film on their surfaces. The sealing glass is then fused to the stem base and lead pins via this oxide film (the oxide film acts as an adhesive), thereby creating an airtight seal between the stem base and lead pins. After sealing, the exposed oxide film on the stem base and lead pins is removed, and then the surface (outer surface) is plated to form a plating film (a) (single or multi-layer plating film). This plating film (a) is composed, for example, of a first layer of Ni plating film and a second layer (finishing layer) of Au plating film. The above describes the plating film (a) formed after the stem base and lead pins are assembled. However, in order to properly form the oxide film described above on the stem base surface, a plating film (b), such as a pure iron plating film, may be formed on the outer surface (base body surface) of the stem base of the present invention as needed. In the above oxidation treatment, an oxide film will be formed on this plating film (b). After assembling the stem base and lead pins and sealing them with sealing glass, the above-described oxide film removal is performed, and the plating film (b) becomes the exposed surface. Typically, the above-described plating film (a) is formed on top of this plating film (b).

[0072] <Lead pin of the present invention> ●Basic configuration of the lead pin of the present invention The lead pin of the present invention is a lead pin that constitutes a matched sealing type glass hermetic seal, wherein the stretching direction of the substrate A described above is defined as the axial direction, and the direction perpendicular to the stretching direction is defined as the radial direction. That is, this lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded bodies, and is characterized in that when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix.

[0073] As described later, the lead pin of the present invention may have a surface treatment coating (mainly a plating coating) on ​​its outer surface (or at least a part of its outer surface). However, in the following description, "lead pin" mainly refers to the pin body excluding such a surface treatment coating. Here, the technical meanings of "[Cr and / or Mo]-Cu composite," "powder metallurgy molded body," "diameter-reduced and drawn material for powder metallurgy molded body," "layered or linear Cr phase and / or Mo phase dispersed in a Cu matrix," and "flake-like, small-piece-like, or granular Cr phase and / or Mo phase dispersed in a Cu matrix" in the lead pin of the present invention are as explained above.

[0074] Figure 6 schematically shows a cross-section of one embodiment of the lead pin of the present invention, with the upper figure of Figure 6 showing a radial cross-section of the lead pin and the lower figure showing an axial cross-section. These cross-sectional figures schematically represent the cross-section of the Cr phase and / or Mo phase formed by stretching Cr particles and / or Mo particles dispersed in a Cu matrix into a needle-like or rod-like shape in the stretching direction. In the axial cross-section of Figure 6 (lower diagram), the short linear elements represent "layered or linear Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph on the right side of Figure 2. Furthermore, in the radial cross-section of Figure 6 (upper diagram), the dot-like elements represent "flake-like, small-piece-like, or granular Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph in the center of Figure 2. The lead pin in Figure 6 is composed of a rod-shaped or linear metal material with the extension direction of the base material A as the axial direction and the direction perpendicular to the extension as the radial direction. Typically, the rod-shaped or linear base material A is cut to an appropriate length to produce pin material, which is then used as the lead pin material.

[0075] As explained earlier, the metal material constituting the lead pin of the present invention is obtained by reducing the surface area (reducing the diameter and stretching) of a material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and stretching it into a rod or wire shape. The stretching direction is the axial direction, and the direction perpendicular to the stretching is the radial direction. Therefore, in the lead pin of the present invention, a Cr phase or a Mo phase is generated in which Cr particles and / or Mo particles dispersed in the Cu matrix are stretched axially into a needle-like or rod-like shape, resulting in the characteristic axial and radial cross-sectional structure described above. Furthermore, a [Cr and / or Mo]-Cu composite having such a characteristic axial and radial cross-sectional structure has unique properties, as described later, particularly properties suitable for lead pins of matched sealing type glass hermetic seals, and such a metal material ([Cr and / or Mo]-Cu composite) has not been known conventionally.

[0076] The radial cross-sectional shape of the rod-shaped or wire-shaped metal material constituting the lead pin of the present invention is not particularly limited, but is usually circular or polygonal (for example, hexagonal, octagonal, or hexagonal cross-sections). There is no strict distinction between rod-shaped material (rod material) and wire-shaped material (wire material), but generally, wire material (wire material) refers to material that can be wound up, while rod-shaped material (rod material) refers to material that cannot be wound up. As described above, this rod-shaped or wire-shaped metal material is obtained by reducing the surface area (reducing the diameter and stretching) of a powder metallurgy molded body to reduce its diameter and stretch it into a rod-shaped or wire-shaped form. By cutting this reduced-diameter and stretched metal material to a predetermined length (however, surface grinding and polishing may be performed as a finishing treatment before or after cutting), the pin material (pin base material) that will be used as the lead pin material of the present invention is obtained.

[0077] ● Characteristics of the lead pin of the present invention As mentioned earlier, the lead pins constituting a matched-type glass hermetic seal are required to have an axial thermal expansion coefficient as close as possible to the thermal expansion coefficient of the sealing glass, to provide high bonding reliability that can maintain a proper adhesion (bonding) state with the sealing glass for a long period of time, and to have sufficiently high axial electrical conductivity. The lead pins of the present invention have the axial and radial cross-sectional structures described above, and therefore possess unique properties (characteristics) that differ from those of conventional lead pins of matched sealing glass hermetic seals. Specifically, the lead pins of the present invention have an axial thermal expansion coefficient < radial thermal expansion coefficient, meaning the axial thermal expansion coefficient is relatively small. As shown in the examples described later, the materials of the present invention all have an extension direction (axial direction of the lead pin) thermal expansion coefficient < extension direction (radial direction of the lead pin) thermal expansion coefficient, meaning the extension direction (axial direction of the lead pin) thermal expansion coefficient is relatively low. Furthermore, the lead pins of the present invention are diameter-reduced drawn materials of powder metallurgy molded bodies, and because they have the extension direction (axial direction) and extension direction (radial direction) cross-sectional structures described above, their radial thermal expansion coefficient is the same in any direction in the radial direction, and the radial thermal expansion coefficient is isotropic.

[0078] Furthermore, the lead pin of the present invention possesses the following characteristics, which are particularly useful and distinctive for lead pins of matched-seal glass hermetic seals: (i) and (ii). (i) The magnitude of the axial thermal expansion coefficient changes depending on the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio during the reduction of diameter of the material due to the reduction of diameter (reduced diameter stretching process). By selecting these blending ratios and reduction ratios, the magnitude of the axial thermal expansion coefficient can be changed (adjusted). For this reason, depending on the thermal expansion coefficient of the sealing glass used, the axial thermal expansion coefficient can be made as close as possible to the thermal expansion coefficient of the sealing glass (in some cases, it can be made to almost match), and by improving the consistency of thermal expansion coefficients with the sealing glass, high bonding reliability with the sealing glass can be obtained. (ii) Those with high axial electrical conductivity, and especially those with optimized characteristics, have significantly higher axial electrical conductivity compared to conventional lead pins, which mainly use Kovar.

[0079] To specifically explain the characteristics of (i) above, the lead pin of the present invention can have its axial thermal expansion coefficient reduced as the proportion of Cr and / or Mo is increased, provided that the reduction ratio of the material during diameter reduction and stretching is the same, and as the reduction ratio of Cr and / or Mo is increased up to approximately 97% during diameter reduction and stretching, provided that the proportion of Cr and / or Mo is the same. As a result, the axial thermal expansion coefficient of the lead pin can be brought as close as possible to (and in some cases nearly identical to) the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the bond between the lead pin and the sealing glass in a harmonized sealing glass hermetic seal.

[0080] To illustrate this using the examples described later, for instance, in the examples, materials No. 5, 10, 15, and 20 of the present invention are made of Cr-Cu composites with a reduction ratio of 90.3% and different Cr content, and the axial thermal expansion coefficient decreases as the Cr content increases. Also, materials No. 24 and 29 of the present invention are made of Mo-Cu composites with a reduction ratio of 97.6% and different Mo content, and materials No. 37 and 39 of the present invention are made of Mo-Cu composites with a reduction ratio of 80% and different Mo content, and in all cases, the axial thermal expansion coefficient decreases as the Mo content increases. On the other hand, for example, materials No. 7 to 12 of the present invention are made of Cr-Cu composites with a Cr content of 45 mass% and different reduction ratios, and materials No. 26 to 29 of the present invention are made of Mo-Cu composites with a Mo content of 40 mass% and different reduction ratios, and in all cases, the axial thermal expansion coefficient decreases as the reduction ratio increases. Therefore, the axial thermal expansion coefficient of the lead pin can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the bond between the lead pin and the sealing glass in a matched sealing glass hermetic seal.

[0081] Furthermore, regarding the characteristics of (ii) described above, the examples described later show that the material of the present invention has significantly higher axial electrical conductivity compared to Kovar (comparative example No. 31), which is widely used in lead pins of conventional matched-seal glass hermetic seals. Furthermore, regarding the axial electrical conductivity, the lead pin of the present invention exhibits a change in axial electrical conductivity depending on the reduction ratio during diameter reduction and stretching. If the proportions of Cr and / or Mo are the same, the axial electrical conductivity increases as the reduction ratio increases up to approximately 97% during diameter reduction and stretching. For example, looking at the materials of the present invention in Examples No. 7 to 12 (Cr content 45 mass%) and No. 26 to 29 (Mo content 40 mass%), the axial electrical conductivity increases as the reduction ratio increases. Therefore, by changing (selecting) the reduction ratio, it is possible to appropriately adjust not only the axial thermal expansion coefficient mentioned above, but also the axial electrical conductivity of the lead pin according to the application equipment. As is clear from the examples, the axial electrical conductivity also changes depending on the component composition of the lead pin (the proportions of Cr and / or Mo), and the axial electrical conductivity increases as the proportions of Cr and / or Mo decrease.

[0082] As described above, the lead pin of the present invention can change (adjust) the magnitude of its axial thermal expansion coefficient. Therefore, depending on the thermal expansion coefficient of the sealing glass used, the axial thermal expansion coefficient can be brought as close as possible to (and in some cases nearly identical to) that of the sealing glass. By improving the compatibility of thermal expansion coefficients with the sealing glass, high bonding reliability with the sealing glass can be obtained. For this reason, compared to conventional lead pins of matched sealing type glass hermetic seals that generally use Kovar, the compatibility of thermal expansion coefficients with the sealing glass is further improved, and the reliability of the airtightness of the matched sealing type glass hermetic seal can be further enhanced. Moreover, compared to conventional lead pins that use Kovar, it has a higher axial electrical conductivity, so the amount of heat generated by the lead pin when energized can be kept low, and the power consumption of the lead pin can also be kept low.

[0083] Furthermore, as described above, since the magnitude of the axial thermal expansion coefficient of the lead pin can be changed (adjusted), when using other metal materials for the stem base in a harmonized sealing glass hermetic seal equipped with the lead pin of the present invention, metal materials that have not been conventionally used in harmonized sealing glass hermetic seals (e.g., carbon steel) can be used. For example, when using carbon steel for the stem base, a sealing glass with a thermal expansion coefficient corresponding to that of carbon steel can be used, and the axial thermal expansion coefficient of the lead pin of the present invention can be matched to the thermal expansion coefficient of this sealing glass. Therefore, by using the lead pin of the present invention, a wide range of material combinations become possible in harmonized sealing glass hermetic seals. For this reason, harmonized sealing glass hermetic seals can be expected to be applied to a wide range of applications as highly reliable glass hermetic seals. In addition, cost reduction can be expected when carbon steel is used as described above. Therefore, the lead pin of the present invention is not merely a replacement for the Kovar lead pins that have been widely used in conventional matched-seal glass hermetic seals, but rather a completely new and extremely useful lead pin that can realize a matched-seal glass hermetic seal with an unprecedentedly high level of "bonding reliability of the seal portion" and "electrical conductivity performance".

[0084] Here, regarding the thermal properties of the metal material constituting the lead pin of the present invention, as mentioned above, the thermal expansion coefficient in the stretching direction (axial direction of the lead pin) is smaller than the thermal expansion coefficient in the direction perpendicular to stretching (radial direction of the lead pin). This is because, as previously stated regarding the stem base, the shear stress at the interface between the Cr phase and / or Mo phase, which has been stretched into a needle-like or rod-like shape by the diameter reduction stretching process, suppresses the expansion of Cu in the stretching direction. However, since the range affected by the shear stress of one Cr phase and / or Mo phase in the cross section perpendicular to stretching is limited, the higher the density of the Cr phase and / or Mo phase in the cross section perpendicular to stretching, that is, the higher the blending ratio (content) of Cr and / or Mo, the smaller the thermal expansion coefficient in the stretching direction tends to be. Furthermore, the shear stress increases as the length of the Cr phase and / or Mo phase in the stretching direction increases. As will be described later, when manufacturing the lead pin (rod-shaped or wire-shaped metal material) of the present invention, a large reduction ratio increases the length of the Cr phase and / or Mo phase in the stretching direction, and the thermal expansion coefficient in the stretching direction decreases. In other words, the larger the reduction ratio, the smaller the thermal expansion coefficient in the stretching direction tends to be. Note that the thermal expansion coefficient perpendicular to the stretching direction tends to increase as the reduction ratio increases. This is because a larger reduction ratio results in a smaller diameter of the Cr phase and / or Mo phase in the direction perpendicular to the stretching direction, and the restraining force of Cu in the direction perpendicular to the stretching direction decreases. From the above, it can be seen that the thermal expansion coefficient in the stretching direction (axial direction of the lead pin) and the direction perpendicular to the stretching direction (radial direction of the lead pin) can be adjusted by selecting the blending ratio (content) of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter. Furthermore, the reason why electrical conductivity increases in the stretching direction (axial direction of the lead pin) as the reduction ratio increases is thought to be because, as the reduction ratio increases, the Cu phase is also stretched in the stretching direction by the Cr phase and / or Mo phase that are stretched in the stretching direction, and the current preferentially flows in the stretching direction.

[0085] Here, the characteristics of each lead pin of the present invention are determined as follows. The axial and radial thermal expansion coefficients are measured using a push-rod type displacement detection method. The average axial and radial thermal expansion coefficients from 30°C to 450°C are calculated by measuring the axial and radial thermal expansion coefficients using the push-rod type displacement detection method, determining the difference in elongation between 30°C and 450°C, and dividing that value by the temperature difference of 420°C (= 450°C - 30°C). Furthermore, the axial electrical conductivity is measured using a commercially available electrical resistance measuring device with the DC four-terminal method (measurement temperature: room temperature, atmosphere: air).

[0086] ● Preferred conditions (configuration and characteristics) for the lead pin of the present invention As described above, the lead pin of the present invention has the following characteristics: (1) axial thermal expansion coefficient < radial thermal expansion coefficient, with a relatively small axial thermal expansion coefficient and isotropic radial thermal expansion coefficient; (2) the magnitude of the axial thermal expansion coefficient can be changed by selecting the blending ratio of Cr and / or Mo and the reduction ratio during diameter reduction stretching; and (3) axial electrical conductivity is sufficiently high. However, the optimal thermal characteristics are an average axial thermal expansion coefficient of 12.0 × 10⁻⁶ from 30°C to 450°C. -6 Below / K, the mean radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10⁻⁶. -6 It is preferable that the temperature is less than or equal to / K and that the average axial thermal expansion coefficient from 30°C to 450°C is less than the average radial thermal expansion coefficient from 30°C to 450°C.

[0087] The average axial thermal expansion coefficient from 30°C to 450°C is 12.0 × 10⁻⁶. -6 If the coefficient of thermal expansion is less than or equal to / K, it is particularly effective in obtaining the effects described above. That is, if the axial average thermal expansion coefficient is within the above range, it will be close to the thermal expansion coefficient of the sealing glass, which is preferable because it makes it easier to obtain bonding reliability with the sealing glass. On the other hand, there are no particularly preferred conditions for the lower limit of the axial average thermal expansion coefficient from 30°C to 450°C, and it is not particularly limited, but in relation to the material composition and reduction ratio, it is generally 7.0 × 10 -6The lower limit is around / K. Furthermore, the axial thermal expansion coefficient can be appropriately adjusted (selected) within the above range depending on the thermal expansion coefficient of the sealing glass used. As mentioned earlier, the average axial thermal expansion coefficient can be adjusted by changing the component composition of the metal material (the blending ratio of Cr and / or Mo) and the reduction ratio when the material is stretched to reduce its diameter. Furthermore, regarding the characteristic of the thermal properties of the lead pins of the present invention, namely that radial thermal expansion coefficient > axial thermal expansion coefficient, in the examples (inventive examples) described later, the difference between the [average axial thermal expansion coefficient from 30°C to 450°C] and the [average radial thermal expansion coefficient from 30°C to 450°C] is 2.0 × 10⁻⁶. -6 It is above / K.

[0088] The reason for using the average thermal expansion coefficient from 30°C to 450°C as the average thermal expansion coefficient in the axial and radial directions is as follows: While sealing glass is used with a glass transition temperature (Tg) in the range of approximately 410 to 560°C, the volume of sealing glass is determined at a temperature around the glass transition temperature - 30°C. Therefore, sealing glass with a glass transition temperature 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 with temperature, 450°C, which is approximately the midpoint of 380 to 530°C, is used as a representative temperature, and the "average thermal expansion coefficient from 30°C to 450°C" is used.

[0089] Furthermore, the lead pin of the present invention has an optimal characteristic of having an axial electrical conductivity of 20.0 × 10⁻⁶. 6 It is preferable that the axial electrical conductivity is 20.0 × 10⁻⁶. 6 If the value is S / m or higher, it is particularly effective in obtaining the effects described above. Note that "electrical conductivity 20.0 × 10 6 When "S / m or more" is replaced with volume resistivity, which is the reciprocal of electrical conductivity, it becomes "volume resistivity of 5.0 μΩ·cm or less". Therefore, in terms of volume resistivity, it is preferable that the axial volume resistivity is 5.0 μΩ·cm or less. High axial electrical conductivity is a particularly useful characteristic for lead pins, but if the axial electrical conductivity is 20.0 × 10⁻⁶ 6A level of S / m or higher represents a significantly higher axial electrical conductivity compared to Kovar and other materials widely used in lead pins of conventionally matched-seal glass hermetic seals, resulting in a particularly low heat generation during energization. Specifically, as shown in the examples described later, the axial electrical conductivity of Kovar (comparative example No. 31), which is widely used in conventional lead pins, is 2.04 × 10⁻⁶. 6 The conductivity is S / m, and the axial electrical conductivity of 50.5 mass% Ni-Fe (comparative example of No. 30) is 2.81 × 10⁻⁶. 6 While the conductivity is S / m, the axial electrical conductivity of the lead pin of the present invention is an order of magnitude larger, indicating that a significantly higher axial electrical conductivity can be obtained. As mentioned earlier, the axial electrical conductivity of this lead pin can also be adjusted by selecting the component composition of the metal material (the proportion of Cr and / or Mo) and the reduction ratio when the material is stretched to reduce its diameter.

[0090] The lead pin of the present invention has the characteristic axial (stretching direction) and radial (perpendicular to stretching direction) cross-sectional structure shown in Figure 2, and therefore possesses the unique properties (characteristics) described above. While the Cr and / or Mo content (mixing ratio) of the [Cr and / or Mo]-Cu composite constituting the lead pin of the present invention is not particularly limited, a total Cr and / or Mo content of 35-60 mass% is particularly effective in obtaining the aforementioned thermal properties. This is because a lower Cr and / or Mo content (total) reduces the restraining force of Cu by the Cr and / or Mo phases, making it difficult to reduce the thermal expansion coefficient of the material, especially the axial thermal expansion coefficient. On the other hand, a higher Cr and / or Mo content (total) reduces the processability of the material, making it difficult to perform surface reduction (diameter reduction stretching) into a rod or wire shape, and also making it difficult to increase the axial electrical conductivity.

[0091] In the [Cr and / or Mo]-Cu composite constituting the lead pin of the present invention, when comparing Cr (Cr phase) and Mo (Mo phase) blended with Cu, there is a tendency that (i) Cr improves the processability (rollability, etc.) of the material compared to Mo, (ii) Mo tends to produce a higher axial electrical conductivity than Cr, and (iii) Mo tends to produce a lower axial thermal expansion coefficient than Cr (the tendencies of (ii) and (iii) above can also be confirmed in the examples described later). Therefore, for example, in a Cr·Mo-Cu composite, the thermal properties can be balanced by adjusting the content and ratio of Cr and Mo according to the required thermal properties, thereby obtaining optimal thermal properties. The diameter size of the lead pin of the present invention varies depending on the glass hermetic seal to be applied, but is typically around φ0.1 to 6 mm.

[0092] The lead pin of the present invention may have a surface treatment coating (mainly a plating coating) on ​​its outer surface (or at least a portion of its outer surface). In matched-seal glass hermetic seals, a surface treatment film (mainly a plating film) is typically formed on the outer surface (or at least a portion of the outer surface) of the lead pin. Examples of this surface treatment film include a plating film formed after the assembly of the lead pin and stem base (a), and a plating film formed as needed before the assembly of the lead pin and stem base (b), as shown below.

[0093] In the manufacture of matched-seal glass hermetic seals, the lead pins and stem bases are typically oxidized before assembly to form an oxide film on their surfaces. The sealing glass is then fused to the lead pins and stem bases via this oxide film (the oxide film acts as an adhesive), thereby creating an airtight seal between the lead pins and stem bases. After sealing, the oxide film on the exposed surfaces of the lead pins and stem bases is removed, and then the surface (outer surface) is plated to form a plating film (a) (single or multi-layer plating film). This plating film (a) is composed, for example, of a first layer of Ni plating film and a second layer (finishing layer) of Au plating film.

[0094] The above describes the plating film (a) formed after the assembly of the lead pin and stem base. However, in order to properly form the oxide film described above on the lead pin surface, a plating film (b), such as a pure iron plating film, may be formed on the outer surface (pin body surface) of the lead pin of the present invention as needed. In the above oxidation treatment, an oxide film will be formed on this plating film (b). After the lead pin and stem base are assembled and sealed with sealing glass, the above-described oxide film removal is performed, and the plating film (b) becomes the exposed surface. Typically, the above-described plating film (a) is formed on top of this plating film (b).

[0095] <Method for manufacturing stem base and lead pin according to the present invention> Next, the method for manufacturing the stem base and lead pin of the present invention will be described. To manufacture the stem base and lead pin of the present invention, first, a rod-shaped or wire-shaped metal material, which is a diameter-reduced and drawn material of a powder metallurgy molded body, is produced. Then, in the case of a plate-shaped stem base, the rod-shaped or wire-shaped metal material is cut radially (i.e., into slices) to cut out a plate material with the stretching direction as the plate thickness direction and the stretching direction perpendicular to the plate surface direction, and this plate material is used as the raw material to manufacture a plate-shaped stem base. In the case of a cylindrical stem base, the rod-shaped or wire-shaped metal material is cut radially (i.e., into slices) to cut out a plate material or block material of a predetermined thickness, the central part of the plate material or block material is hollowed out to process it into a cylindrical material with the stretching direction as the cylindrical axis direction and the stretching direction perpendicular to the cylindrical diameter direction, and this cylindrical material is used as the raw material to manufacture a cylindrical stem base. On the other hand, in the case of lead pins, the above-mentioned rod-shaped or wire-shaped metal material is cut to a predetermined length, and a pin material is cut out with the extension direction as the axial direction and the direction perpendicular to the extension as the radial direction, and the lead pin is manufactured using this pin material as the raw material.

[0096] The rod-shaped or wire-shaped metal material (reduced diameter drawn material) that forms the base of the stem base and lead pin of the present invention can generally be manufactured by reducing the surface area (reducing diameter drawing process) of a material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and then reducing the diameter to draw it into a rod-shaped or wire-shaped form. The rod-shaped or wire-shaped metal material manufactured through such a series of processes will have a structure in which the Cr phase and / or Mo phase are elongated in the axial direction (longitudinal direction) within the Cu matrix, as described above. That is, it will have a cross-sectional structure in the direction of drawing (axial direction) in which layered or linear Cr phases and / or Mo phases are dispersed within the Cu matrix, and a cross-sectional structure in the direction perpendicular to drawing (radial direction) in which flake-like, small-piece-like, or granular Cr phases and / or Mo phases are dispersed within the Cu matrix.

[0097] Therefore, a preferred method for manufacturing stem bases and lead pins of the present invention comprises a step (A) of obtaining a material for reduction of surface area, consisting of a [Cr and / or Mo]-Cu composite, through a step of sintering powder raw materials, and a step (B) of reducing the surface area (reducing diameter stretching) of the material obtained in step (A) to reduce the diameter and stretch it into a rod or wire shape. As will be described later, process (A) also includes cases where the powder raw material is subjected to Cu fusion or densification treatment after sintering, or where the powder raw material is subjected to discharge plasma sintering or hot press sintering.

[0098] In process (A), material for surface reduction can be obtained in various ways, but the basic ways are (i) and (ii) below. Each way should be carried out according to conventional methods. (i) A material for surface reduction made of a [Cr and / or Mo]-Cu composite is obtained by (a1) sintering a molded body (compacted powder) of powder raw materials to make a sintered body, and (a2) subjecting this sintered body to Cu fusion and / or densification treatment. (ii) A material for surface reduction is obtained by subjecting the powder raw material to a process of discharge plasma sintering (SPS sintering) or hot press sintering, which consists of a [Cr and / or Mo]-Cu composite. In the embodiment of (i) above, in step (a1), powder raw material is filled into a mold and molded according to a conventional method, and the molded body (compacted powder) is sintered in a predetermined atmosphere to form a sintered body. Next, in step (a2), at least one of Cu immersion and densification treatment is performed on the sintered body to make it a material for surface reduction processing.

[0099] In the Cu infusion process for sintered bodies, for example, a Cu plate or Cu powder for Cu infusion may be placed on a molded body made from powder raw materials, and it may first be heated to the sintering temperature to sinter it, and then the temperature may be raised to the Cu infusion temperature to carry out the Cu infusion. It is preferable to perform surface grinding (for example, surface grinding using a milling machine or grinding wheel) on the Cu infused body obtained in this process in order to remove any excess pure Cu remaining on the surface. Densification treatment aims to densify a porous sintered body. There are no specific restrictions on the type of treatment, but typical examples include hot extrusion, HIP treatment, hot pressing, and plasma discharge treatment (SPS treatment), and one or more of these can be performed. If the sintered body is not subjected to Cu infiltration, it is preferable to perform this densification treatment to densify the sintered body. On the other hand, the sintered body can be densified by Cu infiltration, and the above-mentioned densification treatment may be performed after this Cu infiltration. In HIP (Hot Isostatic Pressing), one of the densification processes, the sintered body is pressurized (hydrostatically) and heated in a pressure vessel using an inert gas as the pressure medium. In hot press processing, the sintered body is heated and pressurized in a mold. In plasma discharge processing (SPS processing), the sintered body is heated and pressurized in a mold using pulsed current.

[0100] In the embodiment of (ii) above, a dense sintered body is obtained by discharge plasma sintering (SPS sintering) or hot press sintering, and can be used as is as a material for surface reduction processing. In discharge plasma sintering, powdered raw materials packed into a mold are sintered by pulsed current heating while under pressure. In contrast, in hot press sintering, powdered raw materials are placed in a mold and sintered by heating and applying pressure. Therefore, specific embodiments of process (A) include, for example, (a) to (d) below. However, it is not limited to these.

[0101] (a) A material for surface reduction is obtained by molding Cr powder and / or Mo powder, or by molding a mixed powder of Cr powder and / or Mo powder and Cu powder, sintering the molded body to form a sintered body, and then dissolving Cu into the sintered body to obtain a material for surface reduction consisting of a [Cr and / or Mo]-Cu composite. (i) A mixed powder of Cr powder and / or Mo powder and Cu powder is molded, and this molded body is sintered to form a sintered body. This sintered body is then subjected to one of the following densification treatments: hot extrusion, HIP treatment, hot press treatment, or discharge plasma treatment (SPS treatment) to obtain a material for surface reduction made of a [Cr and / or Mo]-Cu composite.

[0102] (c) A material for surface reduction made of a [Cr or / and Mo]-Cu composite is obtained by molding Cr powder and / or Mo powder, or by molding a mixed powder of Cr powder and / or Mo powder and Cu powder, sintering the molded body to make a sintered body, dissolving Cu into the sintered body, and then applying one of the following densification treatments: hot extrusion, HIP treatment, hot press treatment, or discharge plasma treatment (SPS treatment). (e) A material for surface reduction is obtained by discharging plasma sintering or hot press sintering a mixed powder of Cr powder and / or Mo powder and Cu powder, consisting of a [Cr and / or Mo]-Cu composite. The material obtained in process (A) for surface reduction is typically a round bar or a square bar (e.g., a polygonal cross-section).

[0103] Process (B) can be any process as long as the material can be reduced in diameter and stretched into a rod or wire shape by reducing its surface area (diameter reduction stretching). For example, it can be carried out by combining one or more of the following processes: roll rolling, swaging, and hot extrusion. Furthermore, a finish drawing process (wire drawing) may be performed afterward. Roll rolling can be performed using methods such as grooved roll rolling and combined roll rolling. Grooved roll rolling involves reducing the surface area (reducing diameter and stretching) of a material (round bar, square bar, etc.) into a rod or linear shape using grooved rolling rolls. Combined roll rolling involves reducing the surface area (reducing diameter and stretching) of a material (round bar, square bar, etc.) into a rod or linear shape using grooved rolling rolls with multiple stands (e.g., 20 stands or more). Swaging is a type of compression process (cold forging) in which a die is used to compress the material radially, reducing its outer diameter and extending its length (reducing diameter and extending). For example, the material is compressed while the die is rotated, and its length is extended (reducing diameter and extending). In hot extrusion, the material is placed in a container and extruded through the die holes by a ram.

[0104] When performing a finish drawing process (wire drawing), it is usually done as the final surface reduction process (diameter reduction and stretching). However, for example, since the material for the stem base has a large diameter, this finish drawing process may not be performed. In drawing processes, known processing methods such as simple drawing (wet method, dry method) and roller die drawing (CRD) can be used. There are no particular restrictions on the total reduction ratio of the material in process (B), but if the reduction ratio is too small, it becomes difficult to obtain the microstructure of the present invention, so it is desirable that the total reduction ratio of the material in process (B) be 60% or more. Furthermore, there is no particular upper limit on the total reduction ratio of the material in process (B), but there is a practical upper limit depending on the blending ratio of Cr and / or Mo and the manufacturing equipment (processing means for reduction). Here, the reduction ratio (percentage of reduction in cross-sectional area) can be calculated as follows: if the radial cross-sectional area of ​​the material before the reduction process in step (B) is a, and the radial cross-sectional area of ​​the material after the process in step (B) is b, then the reduction ratio (%) = [(ab) / a] × 100.

[0105] The surface of the rod-shaped or wire-shaped metal material obtained in process (B) may have scratches or irregularities due to the surface reduction (diameter reduction and stretching) process in process (B). Depending on the degree of such scratches or irregularities, a gap may form between the material and the sealing glass, for example, in the case of lead pin applications, potentially impairing the sealing state. In particular, in the case of matched sealing type glass hermetic seals, it is preferable to minimize surface irregularities and surface roughness of the metal material to improve adhesion with the sealing glass. Furthermore, it may be necessary to further improve the dimensional accuracy of the outer diameter of the material obtained in process (B). For this reason, in the manufacturing method of the material of the present invention, a further process (C) may be performed as needed, primarily for the purpose of eliminating scratches or irregularities on the material surface, reducing surface roughness, or improving dimensional accuracy, in which the surface of the rod-shaped or wire-shaped metal material obtained in process (B) may be ground or polished. This step (C) may be performed on the rod-shaped or wire-shaped metal material obtained in step (B), or on the rod-shaped or wire-shaped metal material obtained in step (B) that has been cut to a predetermined length, for example, cut for lead pins. There are no particular restrictions on the method of grinding or polishing the material surface in this step (C), but since it deals with relatively small-diameter rod-shaped or wire-shaped materials, it is preferable to use centerless grinding and polishing.

[0106] In the lead pin manufacturing process, the rod-shaped or wire-shaped metal material obtained in step (B) or step (B) + step (C) above is cut to a predetermined length to cut out a pin material with the stretching direction as the axial direction and the direction perpendicular to the stretching direction as the radial direction, and the lead pin is manufactured using this pin material as the raw material. On the other hand, in the manufacturing process for plate-shaped stem bases, the rod-shaped or wire-shaped metal material (however, usually rod-shaped material) obtained in the above process (B) or process (B) + process (C) is cut radially (i.e., sliced ​​into rings), and a plate material is cut out with the axial direction of the metal material being the thickness direction and the radial direction being the surface direction, and a plate-shaped stem base is manufactured using this plate material. In the manufacturing of this plate-shaped stem base, for example, when processing the plate material into a predetermined outer shape or when drilling through holes for inserting lead pins (see Figure 1) in the plate material, the plate material may be punched in the thickness direction. Since this punching is performed in a direction parallel to the stretching direction of the Cr phase, there is no risk of material cracking. Furthermore, in order to reduce the unevenness and surface roughness of the inner surface of the drilled lead pin insertion hole, or to improve the dimensional accuracy of the inner diameter of the hole, a surface grinding or polishing process (C') may be performed on the inner surface of the hole.

[0107] Furthermore, in the manufacturing process for the cylindrical stem base, the rod-shaped or wire-shaped metal material (however, usually rod-shaped material) obtained in the above process (B) or process (B) + process (C) is cut radially (i.e., into rings) to cut out a plate or block material. Then, the central part of this plate or block material is hollowed out to process it into a cylindrical material in which the axial direction of the metal material is the cylindrical axis direction and the radial direction is the cylindrical diameter direction, and the cylindrical stem base is manufactured using this cylindrical material as the base material. In the manufacturing of this cylindrical stem base, for example, when processing the cylindrical material or the plate or block material before processing it into a cylindrical material into a predetermined outer shape, or when hollowing out the central part of the plate or block material, the material may be punched out in the direction of the cylindrical axis. Since this punching is performed in a direction parallel to the stretching direction of the Cr phase, there is no risk of material cracking. Furthermore, for the same purpose as performing step (C) above, in order to reduce the unevenness and surface roughness of the inner surface (inner surface of the hole) of the cylindrical material obtained by hollowing out the plate material or block material as described above, or to improve the dimensional accuracy of the inner diameter of the hole, surface grinding or polishing may be performed on the inner surface of the hole as step (C'). Furthermore, regardless of whether the stem base is plate-shaped or cylindrical, if there are coupled parts such as flange portions 11, 12 or skirt portion 13 relative to the base body 10, as shown in Figures 5(1) and 5(2), necessary processing such as machining is performed.

[0108] In the manufacture of matched-seal glass hermetic seals, the stem base and lead pins are typically oxidized before assembly to form an oxide film on their surfaces. The sealing glass is then fused to the stem base and lead pins via this oxide film (the oxide film acts as an adhesive), thereby creating an hermetic seal between the stem base and lead pins. In order to properly form the aforementioned oxide film on the surface of the stem base or lead pin, which is a [Cr and / or Mo]-Cu composite, a surface treatment film (mainly a plating film), such as a pure iron plating film, may be formed on the outer surface of the stem base or lead pin manufactured as described above, if necessary. In this case, the oxide film will be formed on this surface treatment film by the oxidation treatment described above. Furthermore, in the manufacture of typical matched-seal glass hermetic seals, after assembly and sealing with sealing glass, the exposed surface oxide film of the stem base and lead pins is removed, and then the surface (outer surface) is plated to form a plating film (single or multi-layer plating film). This plating film consists, for example, of a first layer of Ni plating film and a second layer (finishing layer) of Au plating film.

[0109] <Hermet terminal and semiconductor device of the present invention> The hermetic terminal of the present invention is a matched-seal type hermetic terminal (i.e., an hermetic terminal equipped with a matched-seal type glass hermetic seal) and comprises the stem base and / or lead pin of the present invention as described above. Therefore, this matched-seal type hermetic terminal has any of the following features (1) to (3). Furthermore, the semiconductor device of the present invention is a semiconductor device equipped with a matched-seal glass hermetic seal, wherein the matched-seal glass hermetic seal comprises the stem base and / or lead pins of the present invention as described above. Therefore, the matched-seal glass hermetic seal of this semiconductor device also has any of the following features (1) to (3). There are no particular limitations on the semiconductor device to which the present invention applies, but typical examples include semiconductor packages such as TO headers and hermetic packages for sensors.

[0110] (1) The plate-shaped or cylindrical stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded bodies, and when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction of the base in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure in the horizontal direction of the base in which flaky, small-piece or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[0111] (2) The lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material of a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases or / and Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flaky, small-piece or granular Cr phases or / and Mo phases are dispersed in a Cu matrix.

[0112] (3) The plate-shaped or cylindrical stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which Cr phase and / or Mo phase are dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded bodies, and when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction of the base in which layered or linear Cr phase and / or Mo phase are dispersed in the Cu matrix, and a cross-sectional structure in the horizontal direction of the base in which flaky, small-piece or granular Cr phase and / or Mo phase are dispersed in the Cu matrix, and further, The lead pin is made of 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 stretched material for powder metallurgy molded bodies, and when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[0113] The details of the hermetic terminal and the stem base and lead pins of the semiconductor device are as described above. Therefore, the hermetic terminal and semiconductor device of the present invention can each enjoy the effects of the stem base and / or lead pins of the present invention described above. In particular, the seals of hermetic terminals and semiconductor devices having the features of (1) and (3) above are matched sealing type glass hermetic seals, but since compressive stress can be applied from the stem base to the sealing glass, a matched sealing type glass hermetic seal that takes compression sealing into account can be constructed, increasing the mechanical strength of the seal, and thus further improvement in the reliability of bonding with the sealing glass can be expected. Furthermore, hermetic terminals and semiconductor devices having the feature of (3) above are particularly preferred because they can enjoy the effects of the stem base and lead pin of the present invention described above.

[0114] <Study on the bonding reliability of the stem base and lead pin of the present invention> Next, the results of our investigation into the bonding reliability when applying the stem base and lead pin of the present invention to a matched sealing type glass hermetic seal, based on material mechanics considerations, are shown below. In the following description, the stem base will be referred to as the "housing." Also, in the following description (including Tables 1 to 3), "%" in relation to the material composition means "mass%." Furthermore, since the stem base (housing) is assumed to be plate-shaped, the base thickness direction is referred to as the "plate thickness direction," and the base horizontal direction is referred to as the "plate surface direction." As an example (No. 1 in Table 1), we investigated the case where the housing and lead pins of the present invention are applied to a matched-seal glass hermetic seal provided in an airtight terminal. Specifically, we investigated the bonding reliability of a matched-seal glass hermetic seal using the housing and lead pins of the present invention, which are made of a 55% Cr-Cu composite, and ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.) as the sealing glass, using a simplified concentric cylindrical material mechanics approach.

[0115] In the harmonized glass hermetic seals provided by airtight terminals, materials are generally selected so that the thermal expansion coefficients of the housing, sealing glass, and lead pins are as close as possible, thereby achieving high bonding reliability. However, even in the most common harmonized glass hermetic seals where the housing and lead pins are made of Kovar, the thermal expansion coefficients of glass < Kovar are frequently used. This results in compressive stress being applied from the housing to the sealing glass, creating a gap between the lead pins and the glass. The present invention aims to add an element that further enhances reliability by applying compressive force to the sealing glass through the housing. The characteristic of the material of the present invention (housing) that [average thermal expansion coefficient in the thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the surface direction from 30°C to 450°C] means that the housing can apply greater compressive stress to the sealing glass than when Kovar is used for both the housing and lead pins. On the other hand, a simple calculation suggests that an even larger gap will be created between the sealing glass and the lead pins. Therefore, the reliability of harmonized glass hermetic seals (airtight terminals) was examined taking this effect into account.

[0116] Figures 7 and 8 are schematic diagrams (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent members, compressive stress within the seal, etc.) of the harmonized sealing glass hermetic seal used in this study. Figure 7(A) is a schematic longitudinal section of the entire seal, Figure 7(B) is a schematic plan view of the same, and Figure 7(C) is a schematic plan view of the sealing glass. Figure 8(A) is a schematic longitudinal section of the entire seal, Figure 8(B) is a schematic plan view of the housing and sealing glass, and Figure 8(C) is a schematic plan view of the sealing glass and lead pin. The numerical values ​​shown in Figures 7 and 8 represent the average thermal expansion coefficients of each component constituting the seal. For convenience of explanation, the metal material constituting the housing and lead pin of the present invention will be referred to as "55%Cr-Cu material" in the following explanation.

[0117] Because the thermal expansion coefficient of the housing (55%Cr-Cu material) in the direction of the plate surface is greater than that of the sealing glass, the outer radial surface (outer surface) of the sealing glass is subjected to a compressive stress P1 from the inner radial surface (inner surface) of the housing while the sealing glass is cooling from hardening to room temperature. The volume of the sealing glass is determined around [glass transition point - 30°C] relative to the glass transition point where it is fully hardened (the glass transition point of ST-4W mentioned above: 460°C), and at 30°C, the volume is reduced due to thermal expansion. The calculated outer radius R2' of the sealing glass (radius at the outer surface of the sealing glass) is larger than the inner radius R2 of the housing (radius at the inner surface of the housing) due to housing contraction, but it matches the inner radius R2 due to the compressive stress P1 during sealing (see Toshiba Glass Technical Report 26, "On Glass Distortion"). As a result (with constant volume), the inner radius of the sealing glass (radius at the inner surface of the sealing glass) is displaced inward by υ2 (due to compressive strain from the compressive stress P1) to become R3''. The compressive stress P1 acting from the housing to the sealing glass can be predicted by calculating the displacement difference υ2 as a "thick-walled cylinder subjected to external pressure" in the principles of material mechanics.

[0118] The radial thermal expansion coefficient of the lead pin (55% Cr-Cu material) is greater than that of the sealing glass. Therefore, as the sealing glass hardens and cools to room temperature, the lead pin shrinks more radially than the sealing glass, resulting in a calculated gap δ3 (the difference between the calculated inner radius R3' of the sealing glass and the calculated outer radius R3 of the lead pin). If the displacement υ2 toward the inner diameter of the sealing glass is greater than this gap δ3, that is, if R3'' (= R3' - υ2) becomes smaller than R3, then no gap will form at the interface between the sealing glass and the lead pin, potentially achieving reliable bonding. First, it is necessary to set R3'' > 0. In this case, the displacement difference υ3 between R3 and R3'' causes the lead pin to experience a compressive stress P2 from the sealing glass. That is, the sealing glass receives a compressive stress P1 from the housing on its outer radial surface, while simultaneously exerting a compressive stress P2 on the lead pin from its inner radial surface. This compressive stress P2 can be predicted by calculating it from the displacement difference υ3 as a "combined cylinder" in mechanics of materials.

[0119] As an indicator for evaluating bonding reliability, it is necessary to consider the compressive shear stress τ acting on the sealing glass interface in the axial direction of the lead pin and the thickness direction of the housing, and the balance between this compressive shear stress τ and the compressive stresses P1 and P2 in the radial direction of the sealing glass. If the thermal expansion coefficient of the housing in the plate surface direction and the radial thermal expansion coefficient of the lead pin are greater than the thermal expansion coefficient of the sealing glass, the sealing glass will receive a favorable compressive strain after cooling. However, if the temperature rises and falls repeatedly, it will be affected by compression and tension, and the bonding reliability may decrease due to shear stress strain fatigue caused by the difference in thermal expansion coefficients between the thickness direction of the housing, the axial direction of the lead pin, and the sealing glass. For this reason, it is preferable that the thermal expansion coefficients of the housing in the thickness direction, the axial thermal expansion coefficient of the lead pin, and the thermal expansion coefficient of the sealing glass are as small as possible on the compression side of the sealing glass, while it is preferable that the compressive stresses P1 and P2 in the radial direction of the sealing glass be large. Therefore, it can be said that the bonding reliability between the lead pin and housing and the sealing glass is high when the values ​​of τ / P1 and τ / P2 are positive and small (however, it is not a problem if they are negative as long as they are sufficiently small).

[0120] The following shows the results of calculating the displacement differences υ2, υ3 and compressive stresses P1, P2 mentioned above, the thickness-direction shear stress τ1 from the housing to the sealing glass interface, the axial shear stress τ3 from the lead pin to the sealing glass interface, and τ1 / P1 and τ3 / P2. The physical properties of each material used in this calculation will be described later. ●The dimensional changes of the housing (55%Cr-Cu material), sealing glass, and lead pins (55%Cr-Cu material) from 430°C to 30°C are shown below. In Figures 7 and 8, if R1 = 4 mm, R2 = 3 mm, and R3 = 1.6 mm, the dimensions at 430°C and 30°C are as follows. <At 430℃> • Housing inner radius = Sealing glass outer radius = R² * (1 + α¹ * (430℃ - 30℃)) = 3.01608 mm • Inner radius of sealing glass = Outer radius of lead pin = R3 * (1 + α3 * (430℃ - 30℃)) = 1.608576 mm <At 30℃> • Housing outer radius = 4mm = R1 • Housing inner radius = Sealed glass outer radius = 3mm = R2 • Calculated outer radius of the sealing glass: R2' = 3.01608 * (1 - α2 * (430℃ - 30℃)) =3.004619mm →The sealing glass is compressed to 3 mm and subjected to a compressive stress equal to its displacement difference of υ². • Calculated inner radius of the sealing glass: R3' = 1.608576 * (1 - α3 * (430℃ - 30℃)) = 1.602463 mm Lead pin outer radius = 1.6 mm = R3 →δ3=1.602463-1.6=0.002463mm

[0121] ●The volume of the sealing glass is determined near the [glass transition temperature -30°C], and at 30°C, it shrinks due to thermal expansion. While the calculated volume of the sealing glass and the volume after sealing remain constant, assuming the thickness of the sealing glass does not change, At 30°C, the calculated surface area of ​​the sealing glass is as follows: R2'=3.004619mm, R3'=1.602463mm → 20.294mm 2 The outer radius of the sealing glass is 3 mm. The inner radius of the sealing glass is R3” = 1.593786 mm (υ² = 0.008677 mm). ● 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

[0122] ●The compressive stress P2 is as follows: • If lead pins are not present, the inner radius of the sealing glass is R3” = R3' - υ² = 1.593786 mm ·R3>R3”→ R3-R3”=υ3=0.006214mm →The lead pins no longer have a gap with the glass and receive 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

[0123] ●The thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface and the [thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface] / [radial compressive stress P1 from the housing to the sealing glass] are calculated as follows. In Figures 7 and 8, if R1 = 4 mm, R2 = 3 mm, R3 = 1.6 mm, and the housing thickness T1 = 6 mm, the dimensions at 430°C and 30°C are as follows. <At 430℃> Housing thickness = sealing glass thickness; T1' = 6 * (1 + α1 * (430℃ - 30℃)) = 6.02304 mm <At 30℃> Sealing glass thickness; T2' = T1' * (1 - α2 * (430℃ - 30℃)) = 6.000152 mm

[0124] →Compressive strain ε=(T2'-T1) / T1 from the housing to the sealing glass after cooling =0.000025 Compressive stress: Pt1 = Glass modulus * ε = 0.001727 GPa = 1.7277 MPa Compressive force: Ft1 = Pt1 * π * R2 2 =48.85N The thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface is as follows: τ1 = Ft1 / (π*2*R2*T1) = 0.43MPa →Therefore, the [thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface] / [radial-direction compressive stress P1 from the housing to the sealing glass] is as follows: τ1 / P1 = 0.0033

[0125] ●The axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface and the [axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface] / [radial compressive stress P2 from the sealing glass to the lead pin] are calculated as follows. <At 30℃> Thickness of the lead pin in contact with the sealing glass; T3' = T1' * (1 - α3 (430℃ - 30℃)) = 5.999912mm →Compressive strain ε=(T2'-T3') / T3' from the sealing glass to the lead pin after cooling =0.000040 Compressive stress: Pt3 = Glass modulus * ε = 0.002730 GPa = 2.730 MPa Compression force: Ft3 = Pt1 * π * R3 2 =21.96N

[0126] The axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface is as follows: τ3=Ft3 / (π*2*R3*T1)=0.3641MPa Therefore, the axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface / the radial compressive stress P2 from the sealing glass to the lead pin is as follows: τ3 / P2 = 0.0062

[0127] The above calculations were performed using the present invention's housing and lead pins, which are made of 55% Cr-Cu material, and the sealing glass made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). However, similar calculations were performed when the housing, lead pins, and sealing glass were made of other materials. Specifically, for the stem base, the present invention's materials of 45% Cr-Cu, 60% Mo-Cu, and the comparative material Kovar, i.e., 29% Ni-17% Co-Fe (YEF29-17), carbon steel S23C, and SUS430 were used. For the lead pins, the present invention's materials of 60% Mo-Cu, 45% Cr-Cu, and 50% Cr-Cu were used, as well as the comparative materials of 50.5% Ni-Fe, 18.5% Cr-Fe (YFF-18T), and 29% Ni-17% Co-Fe (YEF29-17) were used. The calculation results are shown in Tables 1 to 3, along with the calculation results mentioned above. In Tables 1 to 3, "equivalent to the inventive example" refers to a case in which the housing and / or lead pins use the material of the present invention, and "equivalent to the comparative example" refers to a case in which the housing and lead pins use materials other than the material of the present invention.

[0128] The physical properties of each material used in the calculations in Tables 1 to 3 are as follows. (1) Housing ·55%Cr-Cu material (area reduction rate: 96.8%) Average thermal expansion coefficient in the thickness direction (30-450℃): 9.6 × 10 -6 / K Average coefficient of thermal expansion in plate direction α1 (30-450℃): 13.4×10 -6 / K Young's modulus E1: 206 GPa Poisson's ratio ν1:0.25 ·45%Cr-Cu material (area reduction rate: 96.8%): Table 2 "No.2" Average thermal expansion coefficient in the thickness direction (30-450℃): 10.0 × 10 -6 / K Average coefficient of thermal expansion in plate direction α1 (30-450℃): 15.7×10 -6 / K Young's modulus E1: 198 GPa Poisson's ratio ν1:0.26 ·45%Cr-Cu material (area reduction rate: 90.3%): Table 2 "No.3" Average thermal expansion coefficient in the thickness direction (30-450℃): 11.4 × 10 -6 / K Average coefficient of thermal expansion in plate direction α1 (30-450℃): 16.6×10 -6 / K Young's modulus E1: 198 GPa Poisson's ratio ν1:0.26 ·60%Mo-Cu material (area reduction rate: 80.0%) Average thermal expansion coefficient in the thickness direction (30-450℃): 7.6 × 10 -6 / K Average coefficient of thermal expansion in plate direction α1 (30-450℃): 13.4×10 -6 / K Young's modulus E1: 242 GPa Poisson's ratio ν1:0.33

[0129] • 29% Ni-17% Co-Fe material (YEF29-17): Kovar Average thermal expansion coefficient α1 (30-450℃): 5.5 × 10⁻⁶ -6 / K Young's modulus E1: 152 GPa Poisson's ratio ν 1:0.30 • Carbon steel S23C Average thermal expansion coefficient α1 (20-500℃): 13.9 × 10⁻⁶ -6 / K Young's modulus E1: 200 GPa Poisson's ratio ν1:0.27 SUS430 Average thermal expansion coefficient α1 (0-538℃): 11.3 × 10⁻⁶ -6 / K Young's modulus E1: 200 GPa Poisson's ratio ν1:0.27

[0130] (2) Lead pin ·55%Cr-Cu material (area reduction rate: 96.8%) Average axial thermal expansion coefficient (30-450°C): 9.6 × 10⁻⁶ -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 13.4 × 10 -6 / K Young's modulus E3: 206 GPa Poisson's ratio ν3:0.25 ·60%Mo-Cu material (area reduction rate: 80.0%) Average axial thermal expansion coefficient (30-450°C): 7.6 × 10⁻⁶ -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 13.4 × 10 -6 / K Young's modulus E3: 242 GPa Poisson's ratio ν³:0.33 ·45%Cr-Cu material (area reduction rate: 50.0%) Average axial thermal expansion coefficient (30-450℃): 12.2 × 10 -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 14.3 × 10 -6 / K Young's modulus E3: 198 GPa Poisson's ratio ν³:0.26 ·50%Cr-Cu material (area reduction rate: 83.0%) Average axial thermal expansion coefficient (30-450℃): 10.0 × 10 -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 13.5 × 10 -6 / K Young's modulus E3: 200 GPa Poisson's ratio ν³:0.27

[0131] 50.5% Ni-Fe material Average axial thermal expansion coefficient (30-450℃): 10.3 × 10 -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 11.6 × 10 -6 / K Young's modulus E3: 162 GPa Poisson's ratio ν³:0.30 • 18.5% Cr-Fe material (YFF-18T) Average axial thermal expansion coefficient (30-450℃): 11.4 × 10 -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 11.4 × 10 -6 / K Young's modulus E3: 191 GPa Poisson's ratio ν³:0.26 • 29% Ni-17% Co-Fe material (YEF29-17): Kovar Average axial thermal expansion coefficient (30-450℃): 5.3 × 10⁻⁶ -6 / K mean radial thermal expansion coefficient α3 (30-450℃): 5.3 × 10 -6 / K Young's modulus E3: 152 GPa Poisson's ratio ν³:0.3

[0132] (3) Sealing glass • ST-4W (Glass cord, manufactured by Nippon Electric Glass Co., Ltd.) Average thermal expansion coefficient α² (30-380℃): 9.5 × 10⁻⁶ -6 / K Glass transition temperature Tg: 460℃ Young's modulus E2: 68 GPa Poisson's ratio ν²: 0.21 • ST-13W (Glass cord, manufactured by Nippon Electric Glass Co., Ltd.) Average thermal expansion coefficient α² (30-380℃): 7.6 × 10⁻⁶ -6 / K Glass transition temperature Tg: 510℃ Young's modulus E2: 57 GPa Poisson's ratio ν²: 0.22 • BH-W (Glass cord, manufactured by Nippon Electric Glass Co., Ltd.) Average thermal expansion coefficient α² (30-380℃): 4.6 × 10⁻⁶ -6 / K Glass transition temperature Tg: 470℃ Young's modulus E2: 57 GPa Poisson's ratio ν²: 0.22 • SG354 (Glass cord, manufactured by AGC Corporation) Average thermal expansion coefficient α² (50-350℃): 10.7 × 10⁻⁶ -6 / K Glass transition temperature Tg: 567℃ Young's modulus E2: 68 GPa Poisson's ratio ν²: 0.21 • CK5425 (Glass cord, manufactured by Takara Standard Co., Ltd.) Average thermal expansion coefficient α² (50-350℃): 11.9 × 10⁻⁶ -6 / K Glass transition temperature Tg: 525℃ Young's modulus E2: 57 GPa Poisson's ratio ν²: 0.22

[0133] [Table 1]

[0134] [Table 2]

[0135] [Table 3]

[0136] The combination using Kovar for both the housing and lead pins was treated as a comparative example (conventionally, it is believed that high bonding reliability can be obtained in matched sealing terminals), and the results of calculating τ1 / P1 and τ3 / P2, which are indicators of bonding reliability, were compared with the combination corresponding to the inventive example. The calculation results in Tables 1 to 3 show that the combination using the housing of the present invention (corresponding to the inventive example) yields a greater compressive pressure P1 from the housing to the sealing glass than the comparative example using Kovar, and τ1 / P1 and τ3 / P2 are sufficiently low, indicating that the necessary bonding reliability can be obtained. In particular, as shown in No. 1 and No. 2 in Table 1 and No. 1 in Table 2, by almost matching the average thermal expansion coefficient in the thickness direction of the housing with the average thermal expansion coefficient of the sealing glass, the shear stress generated between the housing and the sealing glass can be made extremely small, and bonding reliability can be maximized. Furthermore, although it is a harmonized sealing type glass hermetic seal, the compression pressure P1 from the housing to the sealing glass allows for the creation of a harmonized sealing type glass hermetic seal that incorporates compression sealing, and it is believed that high bonding reliability can be obtained, enabling the proper adhesion (bonding) state with the sealing glass to be maintained for a long period of time.

[0137] Furthermore, the lead pin used in the present invention (corresponding to the example of the invention) can be judged to provide a compressive pressure P2 from the sealing glass to the lead pin, and that τ3 / P2 is sufficiently low, thus achieving the necessary bonding reliability. In particular, as shown in No. 1 and No. 2 of Table 1, by almost matching the average axial thermal expansion coefficient of the lead pin with the average thermal expansion coefficient of the sealing glass, the shear stress generated between the lead pin and the sealing glass can be made extremely small, thereby maximizing bonding reliability. [Examples]

[0138] The materials of the present invention (rod-shaped or wire-shaped metal materials) were manufactured under the following manufacturing conditions, and their properties were measured. As a comparative material, a material consisting of a [Cr and / or Mo]-Cu composite that had not undergone surface reduction (diameter reduction stretching) was also used. Pure Cu material, 50.5% Ni-Fe material, and 29% Ni-17% Co-Fe material (Kovar; YEF29-17) were used as test materials, and their properties were measured in the same manner as described above. The results, along with the composition (composition, density) and manufacturing conditions (reduction ratio) of the metal materials, are shown in Tables 4 and 5. In the description of this example (including Tables 4 and 5), "%" in relation to the material composition means "mass%".

[0139] Here, since the metal materials in this embodiment are all in the form of a rod or wire, we refer to the axial and radial directions as such, but for the material of the present invention, the axial direction is the stretching direction and the radial direction is the direction perpendicular to the stretching direction. The rod or wire metal material of the present invention can be used as lead pin material as is, in its rod or wire form. Furthermore, a plate-shaped metal material (a plate material in which the axial direction of the rod or wire metal material is the thickness direction and the radial direction is the surface direction) cut out from the rod or wire metal material in the radial direction can be used as is as material for a plate-shaped stem base. Furthermore, a cylindrical metal material (a cylindrical material in which the axial direction of the rod or wire metal material is the thickness direction and the radial direction is the diameter direction) obtained by cutting out a plate or block material from the rod or wire metal material in the radial direction (i.e., in the cross-section), and then hollowing out the central part of this plate or block material can be used as is as material for a cylindrical stem base. Therefore, the axial and radial directions of the material of the present invention correspond to the thickness direction and surface direction of the plate-shaped stem base, and to the axial and radial directions of the cylindrical stem base, respectively.

[0140] Furthermore, although not explicitly shown in Tables 4 and 5, the materials of the present invention all have the cross-sectional structure shown in Figure 2, that is, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the stretching direction (axial direction) in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction (radial direction) in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. In contrast, the comparative material, a [Cr and / or Mo]-Cu composite material that has not undergone surface reduction processing (diameter reduction stretching processing) (surface reduction ratio 0%), naturally does not have such a characteristic cross-sectional structure, but rather a cross-sectional structure like the "soaked body cross-section" in Figure 3.

[0141] (1) Production of material for surface reduction processing Cr powder and / or Mo powder were placed in a mold and pressure-molded, or a mixed powder of Cr powder and / or Mo powder and Cu powder in a predetermined ratio was placed in a mold and pressure-molded to obtain a compact. A pure Cu plate was placed on top of this compact and sintered and Cu fusion was performed in a reducing atmosphere. Specifically, sintering (1000°C, 600 minutes) was performed first to obtain a sintered body, and then the temperature was increased to melt the pure Cu plate, and Cu fusion (1200°C, holding time 180 minutes) was performed to impregnate the sintered body with this Cu to obtain a [Cr and / or Mo]-Cu composite. Using a milling machine, the Cu remaining on the surface of the [Cr and / or Mo]-Cu composite was cut off and the shape was refined to obtain a material (rod-shaped material) for surface reduction of a predetermined size.

[0142] (2) Fabrication of the material of the present invention by surface reduction (diameter reduction stretching) (2.1) In the case of the materials of the present invention in Examples No. 33 to 35 A material for surface reduction, shaped into an octagonal prism (50 mm in diameter) by milling, is then subjected to surface reduction (diameter reduction and stretching) to an outer diameter of φ15 mm by groove roll rolling and subsequent swaging. This is followed by surface reduction (diameter reduction and stretching) to a 3.7 mm thick prism (octagonal in diameter) by combined roll rolling. Finally, a finish drawing process consisting of roller die drawing (CRD) and simple drawing (wet cold drawing) is performed to further reduce the surface size (diameter reduction and stretching), resulting in the material of the present invention with an outer diameter of φ3.2 mm. (2.2) In the case of other materials of the present invention A material for surface reduction, shaped into a 16-sided prism (20.7 mm in diameter) by milling, was subjected to surface reduction (diameter reduction and stretching) to an outer diameter of φ3.7 mm by swaging and subsequent combined roll rolling. Further surface reduction (diameter reduction and stretching) was performed using a two-stage roller die drawing (CRD) process to obtain the material of the present invention with an outer diameter of φ3.2 mm.

[0143] (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 (which becomes the thermal conductivity in the base thickness direction for stem bases) were determined using the measurement and calculation methods described earlier. For the measurement of axial electrical conductivity (and volume resistivity), an "Electrical Resistivity Measuring Device TER-2000RH Special Type" manufactured by Advance Engineering was used. Furthermore, for samples with the same material composition but different reduction ratios, material for the other samples was taken during the reduction process of the sample with the largest reduction ratio, processed into φ3.2 mm samples using centerless grinding, and used for each measurement.

[0144] According to Tables 4 and 5, the material of the present invention has a certain level of radial thermal expansion coefficient (in the case of a stem base, the base horizontal thermal expansion coefficient; the same applies hereinafter), while its axial thermal expansion coefficient (in the case of a stem base, the base thickness direction thermal expansion coefficient; the same applies hereinafter) is considerably smaller than that of the radial thermal expansion coefficient, and the sealing glass (usually 8-11 × 10) -6 It can be seen that the thermal expansion coefficient can be made close to approximately 1 / K. For example, as can be seen from the present invention examples "No. 5, 10, 15, 20", "No. 24, 29", "No. 37, 39", "No. 7~12", "No. 26~29", the present invention allows for adjustment of the axial thermal expansion coefficient by selecting the blending ratio (content) of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter. Therefore, the axial thermal expansion coefficient can be made as close as possible to the thermal expansion coefficient of the sealing glass to that of the sealing glass.

[0145] Furthermore, the material of the present invention exhibits significantly higher axial electrical conductivity compared to conventional lead pin materials such as Kovar and 50.5% Ni-Fe, and significantly higher axial thermal conductivity (thermal conductivity in the base thickness direction in the case of stem bases; the same applies hereinafter) compared to conventional stem base materials such as Kovar and carbon steel (thermal conductivity: approximately 40-60 W / m·K). In addition, as can be seen from examples of the present invention such as "No. 7-12" and "No. 26-29," the axial electrical conductivity and axial thermal conductivity of the material of the present invention can be changed not only by changing the component composition but also by changing the reduction ratio during diameter reduction stretching, so that the axial electrical conductivity and axial thermal conductivity can be adjusted according to the application equipment. From the above points, it can be understood that the stem base of the present invention has high reliability in bonding with the sealing glass and also has excellent heat dissipation performance in the thickness direction. Furthermore, it can be understood that the lead pins of the present invention have high reliability in bonding with the sealing glass, generate little heat when energized, and reduce power consumption at the lead pins.

[0146] [Table 4]

[0147] [Table 5] [Explanation of Symbols]

[0148] 1 Stem base 2 lead pins 3. Sealing glass 4 Through holes 10 Main Unit 11,12 Flange section 13 Skirt section

Claims

1. A plate-shaped or cylindrical stem base constituting a harmonized sealing glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded articles, and when the cross-sectional structure is observed with an optical microscope, the Cu matrix contains layered or linear Cr phases and / or Mo phases dispersed within it (including cases where both "layered Cr phases and / or Mo phases" and "linear Cr phases and / or Mo phases" are mixed in the Cu matrix), and the cross-sectional structure in the base thickness direction (however, in the case of a plate-shaped stem base, the plate thickness direction; in the case of a cylindrical stem base, the cylindrical axis direction; the same applies hereinafter) and the Cu matrix A stem base for a compatible sealing type glass hermetic seal, characterized in that it has a cross-sectional structure in the horizontal direction of the base (however, in the case of a plate-shaped stem base, the direction parallel to the plate surface; in the case of a cylindrical stem base, the direction of the cylinder; the same applies hereinafter) in which flaky, small-piece, or granular Cr phase and / or Mo phase are dispersed in the Cu matrix (however, including cases in which two or more of the following are mixed in the Cu matrix):

2. The average thermal expansion coefficient in the thickness direction of the base from 30°C to 450°C is 12.0 × 10⁻⁶. －６ Below / K, the average horizontal thermal expansion coefficient of the base from 30°C to 450°C is 18.0 × 10⁻⁶. －６ A stem base for a harmonized sealing glass hermetic seal according to claim 1, characterized in that the temperature is less than or equal to / K and [average thermal expansion coefficient in the base thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the base horizontal direction from 30°C to 450°C].

3. The stem base of a harmonized sealing type glass hermetic seal according to claim 1, characterized in that the thermal conductivity in the thickness direction of the base is 180 W / m·K or more.

4. The stem base of a matched sealing type glass hermetic seal according to claim 2, characterized in that the thermal conductivity in the thickness direction of the base is 180 W / m·K or more.

5. The stem base of a harmonized sealing glass hermetic seal according to claim 1, characterized in that the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

6. The stem base of a matched sealing type glass hermetic seal according to claim 1, characterized in that it has a plated coating on at least a portion of its outer surface.

7. Lead pins constituting a matched sealing type glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretching material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix (including cases where both "layered Cr phases and / or Mo phases" and "linear Cr phases and / or Mo phases" are mixed in the Cu matrix), and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix (including cases where two or more of "flaky Cr phases and / or Mo phases," "small-piece Cr phases and / or Mo phases," and "granular Cr phases and / or Mo phases" are mixed in the Cu matrix), and is a lead pin for a compatible sealing type glass hermetic seal.

8. The average axial thermal expansion coefficient from 30°C to 450°C is 12.0 × 10⁻⁶. －６ Below / K, the mean radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10⁻⁶. －６ Lead pin of a harmonized sealing glass hermetic seal according to claim 7, characterized in that the temperature is less than or equal to / K and the average axial thermal expansion coefficient from 30°C to 450°C is less than the average radial thermal expansion coefficient from 30°C to 450°C.

9. The axial electrical conductivity is 20.0 × 10 ６ Lead pin of a matched sealing type glass hermetic seal according to claim 7, characterized in that it is S / m or greater.

10. The axial electrical conductivity is 20.0 × 10 ６ Lead pin of a matched sealing type glass hermetic seal according to claim 8, characterized in that it is S / m or greater.

11. Lead pin for a harmonized sealing glass hermetic seal according to claim 7, characterized in that the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

12. Lead pin of a matched sealing type glass hermetic seal according to claim 7, characterized in that it has a plated coating on at least a portion of its outer surface.

13. In a matched, sealed, hermetically sealed terminal, An airtight terminal characterized by comprising a stem base according to any one of claims 1 to 6.

14. In a matched, sealed, hermetically sealed terminal, An airtight terminal characterized by comprising a lead pin as described in any one of claims 7 to 12.

15. In a matched, sealed, hermetically sealed terminal, An airtight terminal comprising a stem base according to any one of claims 1 to 6 and a lead pin according to any one of claims 7 to 12.

16. In a semiconductor device equipped with a matched-seal glass hermetic seal, A semiconductor device characterized in that the matched sealing glass hermetic seal comprises a stem base according to any one of claims 1 to 6.

17. In a semiconductor device equipped with a matched-seal glass hermetic seal, A semiconductor device characterized in that the matched sealing glass hermetic seal comprises the lead pins described in any one of claims 7 to 12.

18. In a semiconductor device equipped with a matched-seal glass hermetic seal, A semiconductor device characterized in that the matched sealing glass hermetic seal comprises a stem base according to any one of claims 1 to 6 and lead pins according to any one of claims 7 to 12.

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