CN103354950A - Cover material for airtight sealing, package for housing electronic components, and method for manufacturing cover material for airtight sealing - Google Patents

Abstract

Provided is a cover material for airtight sealing that uses a glass material that does not contain Pb and that can sufficiently assure airtightness of a package for housing electronic components. This cover material for airtight sealing (1, 201) is formed from a metal base material (12, 212) containing a metal material that contains at least Cr, a coating layer(s) (13, 213a, 213b) that is formed from a Cr oxide film and formed on the surface of the metal base material, and a joining layer (11) for joining the metal base material on which the coating layer is formed with an electronic component housing material (30), said joining layer (11) formed on the surface of the coating layer and formed from a glass material that does not contain Pb.

Description

Method for producing hermetically sealed lid material, container for housing electronic components, and hermetically sealed lid material

technical field

This invention relates to the manufacturing method of the lid material for airtight sealing, the container (package) for housing electronic components, and the lid material for airtight sealing.

Background technique

Conventionally, there is known an electronic component storage container that hermetically seals a cover material and an electronic component storage member made of a ceramic material in a state where electronic components are stored, using a bonding layer made of Pb-containing solder or glass. However, it is not preferable to use solder or glass containing Pb in the container for housing electronic components, since Pb is a harmful substance, and a bonding material that does not contain Pb is required.

Moreover, when a ceramic material is used for a cover material, the thickness of a cover material becomes large, and there arises the disadvantage that the container for electronic component storage enlarges. Therefore, it is required to use a metal material that can reduce the thickness of the cover material more than a ceramic material as the cover material.

Here, an electronic component housing container is proposed that hermetically seals a lid material made of a metal material and an electronic component housing member made of a ceramic material using a bonding layer made of a Pb-free Au-20Sn alloy. Since this Au-20Sn alloy has a low melting point (approximately 280° C.), it is possible to suppress deterioration of electronic components contained therein due to heat. However, Au is expensive, and an alternative material of Au-20Sn alloy is required.

In view of the above, a container for electronic component storage is currently proposed, which uses a bonding layer made of a glass material instead of an Au-20Sn alloy, and hermetically seals a cover material made of a metal material and an electronic part made of a ceramic material. Parts storage member. Such an electronic component housing container is disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-26679.

The above-mentioned Japanese Patent Application Laid-Open No. 2002-26679 discloses a surface mount type crystal resonator (electronic component storage container), which includes a crystal resonator, a recess for storing the crystal resonator, and a frame formed around the recess. Ceramic containers, and metal lids. The metal cover of this surface-mounted crystal vibrator is made of a Fe-based alloy containing Ni plating (Kovar) or an Fe-based alloy containing 42% by mass of Ni and 6% by mass of Cr and Fe. Alloy (426 alloy) composition. In the surface mount type crystal resonator, the frame of the ceramic container and the metal cover are bonded by low-melting glass, whereby the crystal resonator is hermetically sealed in the ceramic container.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2002-26679

Contents of the invention

The problem to be solved by the invention

However, in the surface-mounted crystal vibrator disclosed in the above-mentioned Japanese Patent Laid-Open No. 2002-26679, the metal cover is composed of Ni-plated Fe-based alloy (Kovar-Fe-based nickel-cobalt alloy) and 426 alloy. Therefore, the metal on the surface of the metal cover layer and the low-melting glass may not be able to adhere sufficiently. In this case, there is a problem that the airtightness of the surface mount type crystal resonator (ceramic container) cannot be sufficiently ensured.

The present invention was made in order to solve the above-mentioned problems, and an object of the present invention is to provide an airtight sealing cover material, an electronic A method of manufacturing a container for storing parts and a cover material for airtight sealing.

The method used to solve the problem and the effect of the invention

The airtight sealing lid material according to the first aspect of the present invention is used in an electronic component storage container including an electronic component storage member made of a ceramic material for storing electronic components, and the airtight sealing lid material comprises: A metal substrate of a metal material containing at least Cr; a coating layer formed on the surface of the metal substrate and composed of a Cr oxide film; and a glass material not containing Pb formed on the surface of the coating layer, In addition, it is used as a bonding layer for bonding the metal substrate on which the coating layer is formed and the electronic component housing member.

The hermetic sealing cover material according to the first aspect of the present invention, as described above, is provided with a coating layer composed of a Cr oxide film formed on the surface of the metal substrate; and a coating layer formed on the surface of the coating layer. Composed of Pb-free glass material and used to join the metal base material on which the cladding layer is formed and the bonding layer of the electronic component housing member, it is possible to make the Cr oxide film constituting the cladding layer and the glass material constituting the bonding layer Sufficient close contact allows the metal substrate and the electronic component housing member to be sufficiently bonded. Thereby, the airtightness of the electronic component storage container can fully be ensured using the glass material which does not contain Pb. In addition, by providing a metal base material containing a metal material containing at least Cr, the thickness of the hermetic sealing cover material can be reduced compared with the case where a ceramic material is used as the base material, so that it is possible to suppress the increase in the size of the electronic component housing container. . In addition, the metal base material includes a metal material containing at least Cr, whereby a coating layer composed of a Cr oxide film can be easily formed on the surface of the metal base material.

The hermetic sealing lid material according to the first aspect is preferably configured such that the thermal expansion coefficient α1 (/°C) of the joining layer and the thermal expansion coefficient α2 (/°C) of the metal substrate are equal to each other in a temperature range of 30°C to 250°C. The relationship of -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 is satisfied. According to such a configuration, when the temperature is lowered from the temperature at which the metal substrate and the bonding layer are bonded, the stress generated in the bonding layer made of the glass material can be reduced, and therefore, the occurrence of cracks (cracks) in the bonding layer made of the glass material can be suppressed. ).

In the hermetic sealing lid material according to the first aspect, the coating layer preferably has a thickness of 0.3 μm or more. According to such a configuration, a sufficient thickness of the cladding layer can be ensured, so that the Cr oxide film constituting the cladding layer and the glass material constituting the bonding layer can be reliably adhered to each other.

In the hermetic sealing lid material according to the first aspect, the metal base material preferably contains an Fe-based alloy containing Ni, 3% by mass to 6% by mass of Cr, and Fe. According to such a configuration, the metal base material is made of an Fe-based alloy containing 3% by mass or more of Cr, whereby a coating layer made of a Cr oxide film can be reliably formed on the surface of the metal base material. In addition, when the metal base material is composed of an Fe-based alloy containing 6% by mass or less of Cr, the increase in the thermal expansion coefficient of the metal base material due to the excessive content of Cr can be suppressed, and the thermal expansion coefficient of the metal base material and the bonding layer can be suppressed. Significant difference in the coefficient of thermal expansion. Thereby, it is possible to suppress occurrence of cracks or the like caused by differences in thermal expansion in the bonding layer or the metal base material. In addition, the metal substrate contains Ni, which can reduce the thermal expansion coefficient of the metal substrate, so that the thermal expansion coefficient of the metal substrate can be brought closer to the thermal expansion coefficient of the bonding layer made of a glass material having a smaller thermal expansion coefficient than general metal materials.

In this case, it is preferable that the metal substrate is composed of an Fe-based alloy containing 42 mass % of Ni, 3 mass % to 6 mass % of Cr, and Fe. According to such a configuration, the metal base material contains 42% by mass of Ni, and the thermal expansion coefficient of the metal base material can be reliably reduced. Therefore, the thermal expansion coefficient of the metal base material can be reliably brought close to that of a joint made of a glass material with a small thermal expansion coefficient. The coefficient of thermal expansion of the layer. In addition, the metal base material is composed of an Fe-based alloy containing 42% by mass of Ni and 3% by mass to 6% by mass of Cr, whereby the thermal expansion coefficient α1 of the bonding layer and the thermal expansion coefficient α2 of the metal base material can be configured to be Since the relationship of -15×10 ^-7 ≤ α2 - α1 ≤ 5×10 ^-7 is satisfied, it is possible to reliably suppress the occurrence of cracks in the bonding layer made of the glass material. In addition, the inventors of the present application have confirmed the above viewpoint through experiments.

In the hermetic sealing lid material according to the first aspect, the coating layer is preferably formed on the surface of the metal substrate on which the bonding layer is disposed and on the surface of the metal substrate on the opposite side to the side on which the bonding layer is disposed. According to such a configuration, unlike the case where the coating layer is formed only on either surface of the metal base material, it is possible to prevent the joint layer from being erroneously formed on the surface of the metal base material on which the coating layer is not formed.

In the hermetic sealing lid material of the first aspect above, it is preferable that the metal base material is arranged on the side of the bonding layer, and it is composed of a composite ( clad) material composition. According to such a configuration, the thermal expansion coefficient of the metal base can be easily adjusted by joining different types of metal materials having different thermal expansion coefficients, compared to a case where the metal base is composed of only one layer. In addition, by arranging the first layer containing at least Cr on the bonding layer side, a coating layer made of a Cr oxide film can be easily formed on the surface of the metal substrate corresponding to the region where the bonding layer is formed.

In this case, it is preferable that the coefficient of thermal expansion of the first layer is larger than that of the bonding layer, and that the coefficient of thermal expansion of the second layer be smaller than that of the bonding layer. According to such a configuration, by adjusting the thickness of the first layer and the thickness of the second layer, the thermal expansion coefficient of the metal base material as a whole can be brought close to the thermal expansion coefficient of the bonding layer.

In the hermetic sealing cover material in which the above-mentioned metal base material is composed of a composite material including at least a first layer and a second layer, it is preferable that the first layer of the metal base material is made of Cr containing Ni, 3% by mass or more and 6% by mass or less. , and Fe-based alloy composition. According to such a configuration, a coating layer made of a Cr oxide film can be reliably formed on the surface of the metal substrate corresponding to the region where the bonding layer is formed. In addition, the first layer of the metal substrate is made of an Fe-based alloy containing Ni, thereby reducing the thermal expansion coefficient of the first layer, thereby making the thermal expansion coefficient of the metal substrate close to that of a glass material having a small thermal expansion coefficient. Coefficient of thermal expansion of the bonding layer.

In the above-mentioned lid material for airtight sealing in which the metal base material is composed of a composite material including at least a first layer and a second layer, it is preferable that the metal base material is composed of a composite material including a layer comprising at least A first layer of Cr; disposed on the opposite side of the first layer from the bonding layer, comprising a second layer of a metal material different from the first layer; and disposed on the opposite side of the second layer from the first layer, comprising at least The third layer of Cr. According to such a configuration, each of the first layer and the third layer located on the surface side of the metal substrate is constituted to contain at least Cr, and therefore, the The surface of the third layer and the surface of the third layer on the opposite side to the second layer) are respectively formed with a coating layer composed of a Cr oxide film. In this way, unlike the case where the coating layer is formed only on either surface of the metal base material, it is possible to prevent the joint layer from being erroneously formed on the surface of the metal base material on which the coating layer is not formed.

In the hermetic sealing cover material in which the above-mentioned metal substrate is composed of a composite material including the first layer, the second layer and the third layer, it is preferable that both the first layer and the third layer are made of Ni, 3% by mass or more than 6% by mass. % less than Cr, and Fe-based alloy composition of Fe. According to such a configuration, since both the first layer and the third layer of the metal substrate are made of the Fe-based alloy containing Ni, the thermal expansion coefficients of the first layer and the third layer can be reduced. Thereby, the thermal expansion coefficient of the metal substrate as a whole can be brought close to the thermal expansion coefficient of the bonding layer made of a glass material having a small thermal expansion coefficient.

In the hermetic sealing cover material in which the first layer and the third layer are composed of Fe-based alloys, it is preferable that both the first layer and the third layer are made of Fe containing 42% by mass of Ni, 6% by mass of Cr, and Fe. The second layer is composed of an Fe-based alloy containing 42% by mass of Ni and Fe. According to such a configuration, since the first layer, the second layer, and the third layer of the metal substrate are all made of an Fe-based alloy containing 42% by mass of Ni, the size of the first layer, the second layer, and the third layer can be reliably reduced. The coefficient of thermal expansion of the layer. Thereby, the thermal expansion coefficient of the metal substrate can be brought close to the thermal expansion coefficient of the bonding layer made of a glass material having a small thermal expansion coefficient. In addition, both the first layer and the third layer are composed of common Fe-based alloys containing 42% by mass of Ni, 6% by mass of Cr, and Fe, and the second layer is composed of common Fe-based alloys containing 42% by mass of Ni and Fe. Fe-based alloy composition, thus, it is possible to use an easily available Fe-based alloy to form a coating layer composed of a Cr oxide film on the surface of the metal substrate corresponding to the region where the bonding layer is formed, and to make the metal substrate The coefficient of thermal expansion of the material is close to that of the bonding layer made of glass material.

In the hermetic sealing lid material in which the first layer and the third layer are made of an Fe-based alloy, it is preferable that the total thickness of the first layer and the third layer is 50% or more of the thickness of the entire metal base material. According to such a configuration, the thermal expansion coefficient α1 of the bonding layer and the thermal expansion coefficient α2 of the metal substrate can be configured to satisfy the relationship of -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 , so that the The bonded layer of material is cracked. The inventors of the present application also conducted experiments to confirm this point.

A second aspect of the present invention is an electronic component storage container comprising a hermetic sealing cover material and an electronic component storage member, wherein the hermetic sealing cover material includes a metal base material having a metal material containing at least Cr, and A coating layer composed of a Cr oxide film formed on the surface of the metal base material, and a bonding layer formed on the surface of the coating layer composed of a Pb-free glass material; the electronic component housing member is formed via the bonding layer and A coated metal substrate is bonded and constructed of a ceramic material for housing electronic components.

In the container for storing electronic components according to the second aspect of the present invention, as described above, the hermetic sealing cover material includes: a coating layer composed of a Cr oxide film formed on the surface of the metal base material, and a coating layer formed on the surface of the coating layer. The bonding layer formed on the Pb-free glass material, and the electronic component housing member is configured to be bonded to the metal base material on which the cladding layer is formed via the bonding layer, thereby enabling oxidation of Cr constituting the cladding layer. Since the film is sufficiently adhered to the glass material constituting the bonding layer, the metal substrate and the electronic component housing member can be sufficiently bonded. Thereby, the airtightness of the electronic component storage container can be fully ensured using the glass material which does not contain Pb. In addition, the lid material for airtight sealing includes a metal base material having a metal material containing at least Cr, thereby, compared with the case where a ceramic material is used for the base material, the thickness of the lid material for airtight sealing can be reduced, so it is possible to Suppresses enlargement of electronic component storage containers. In addition, when the metal base has a metal material containing at least Cr, a coating layer composed of a Cr oxide film can be easily formed on the surface of the metal base.

In the electronic component housing container according to the second aspect, it is preferable that the thermal expansion coefficient α1 (/°C) of the bonding layer and the thermal expansion coefficient α3 (/°C) of the electronic component housing member be equal to each other in a temperature range of 30°C to 250°C. The relationship of 0≤α1-α3≤10×10 ^-7 is satisfied. According to such a configuration, when the temperature is lowered from the temperature at which the bonding layer and the electronic component housing member are bonded, the stress generated in the bonding layer made of glass material can be reduced, and therefore, the occurrence of cracks in the bonding layer made of glass material can be suppressed. (crack).

In this case, it is preferable to configure such that the thermal expansion coefficient α1(/°C) of the bonding layer and the thermal expansion coefficient α3(/°C) of the electronic component housing member satisfy 0≤α1-α3≤in the temperature range of 30°C to 250°C 10×10 ^-7 relationship, and the thermal expansion coefficient α1 (/°C) of the bonding layer and the thermal expansion coefficient α2 (/°C) of the metal substrate satisfy -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 relation. According to such a configuration, by satisfying 0≦α1-α3≦10×10 ^-7 , it is possible to configure such that no stress is applied or a slight tensile stress is applied to the electronic component housing member side of the bonding layer. In addition, by satisfying -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 , it can be configured that no stress is applied or a slight tensile stress is applied to the metal substrate side of the joining layer. Thus, even when stress is applied to the bonding layer, tensile stress from both the metal base material and the electronic component housing member is applied to the bonding layer disposed between the metal base material and the electronic component housing member, so Unlike the case where stress is applied to the bonding layer from only any one of the metal base material and the electronic component housing member, generation of cracks in the bonding layer can be suppressed.

A method of manufacturing an airtight lid material according to a third aspect of the present invention is an airtight lid used in an electronic component storage container including an electronic component storage member made of a ceramic material for accommodating electronic components A method for producing a material comprising: oxidizing Cr of the metal base material on the surface of the metal base material including a metal material containing at least Cr to form a coating layer composed of an oxide film of Cr; and A step of forming, on the surface of the coating layer, a bonding layer made of a Pb-free glass material for bonding the metal substrate on which the coating layer is formed and the electronic component housing member.

The method for manufacturing an airtight lid material according to the third aspect of the present invention, as described above, includes the following steps: oxidizing Cr of the metal base material on the surface of the metal base material containing at least Cr to form Cr A step of forming a cladding layer made of an oxide film; and forming a bonding layer made of a Pb-free glass material on the surface of the cladding layer for bonding the metal base material on which the cladding layer is formed and the electronic component housing member As a result, the Cr oxide film constituting the coating layer and the glass material constituting the bonding layer can be sufficiently adhered to each other, so that the metal substrate and the electronic component housing member can be sufficiently bonded. Thereby, the airtightness of the electronic component storage container can be fully ensured using the glass material which does not contain Pb. In addition, by using a metal base material containing a metal material containing at least Cr, compared with the case where a ceramic material is used in the base material, the thickness of the lid material for airtight sealing can be reduced, so the electronic component storage container can be suppressed. Upsizing. In addition, the metal base material includes a metal material containing at least Cr, whereby a coating layer made of a Cr oxide film can be easily formed on the surface of the metal base material.

In the method for manufacturing an airtight sealing cover material according to the third aspect, preferably, the step of forming the cladding layer includes adding a metal containing an Fe-based alloy containing Ni, 3% by mass to 6% by mass, and Fe-based alloy. A step of forming a coating layer composed of a Cr oxide film on the surface of a metal base material. According to such a configuration, the metal base material is composed of an Fe-based alloy containing 3% by mass or more of Cr, whereby a coating layer composed of a Cr oxide film can be reliably formed on the surface of the metal base material. In addition, when the metal base material is composed of an Fe-based alloy containing 6% by mass or less of Cr, an increase in the thermal expansion coefficient of the metal base material due to an excessive content of Cr can be suppressed, and the thermal expansion coefficient of the metal base material and the thermal expansion of the bonding layer can be suppressed. The coefficients are significantly different. Accordingly, it is possible to suppress occurrence of cracks (cracks) or the like in the bonding layer or the metal base material due to differences in thermal expansion. In addition, the metal base contains Ni, whereby the thermal expansion coefficient of the metal base can be reduced, and the thermal expansion coefficient of the metal base can be brought close to the thermal expansion coefficient of the bonding layer made of a glass material smaller than that of the metal material.

In this case, it is preferable that the step of forming a coating layer composed of an oxide film of Cr includes preferentially oxidizing Cr of the metal substrate under a humid hydrogen atmosphere at a temperature of 1000° C. to 1150° C., thereby , a step of preferentially forming a coating layer composed of a Cr oxide film on the surface of the metal substrate. According to such a structure, the thickness of the coating layer which consists of a Cr oxide film can be reliably ensured sufficiently.

In the above-mentioned method for producing an airtight lid material having a coating layer composed of an oxide film of Cr preferentially formed, it is preferable to preferentially form a coating layer composed of an oxide film of Cr, comprising: It is defined as a step of preferentially forming a coating layer composed of an oxide film of Cr in a humid hydrogen atmosphere having a partial pressure higher than the partial pressure capable of oxidizing Fe and Ni and lower than the partial pressure capable of oxidizing Cr. According to such a configuration, it is easy to preferentially oxidize only Cr, so that the thickness of the coating layer formed of the Cr oxide film formed on the surface of the metal substrate can be ensured more reliably.

Description of drawings

FIG. 1 is a perspective view showing the structure of an airtight sealing cover material according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view along line 300-300 of FIG. 1 .

3 is a perspective view showing the structure of the electronic component housing container according to the first embodiment of the present invention.

FIG. 4 is a cross-sectional view along line 400-400 of FIG. 3 .

Fig. 5 is a cross-sectional view for explaining the manufacturing process of the hermetic sealing cover material according to the first embodiment of the present invention.

Fig. 6 is a cross-sectional view illustrating a manufacturing process of the electronic component housing container according to the first embodiment of the present invention.

FIG. 7 is a table showing experimental results of thermal expansion coefficient measurement performed to confirm the effect of the first embodiment of the present invention.

FIG. 8 is a graph showing experimental results of thermal expansion coefficient measurement performed to confirm the effect of the first embodiment of the present invention.

FIG. 9 is a graph showing experimental results of thermal expansion coefficient measurement performed to confirm the effect of the first embodiment of the present invention.

10 is a table showing experimental results of thickness measurement of an oxide film layer performed to confirm the effect of the first embodiment of the present invention.

11 is a table showing experimental results of thickness measurement of an oxide film layer performed to confirm the effect of the first embodiment of the present invention.

12 is a cross-sectional view showing an experimental method of wettability measurement for confirming the effect of the first embodiment of the present invention.

13 is a cross-sectional view showing an experimental method of wettability measurement for confirming the effect of the first embodiment of the present invention.

FIG. 14 is a graph showing experimental results of wettability measurements performed to confirm the effects of the first embodiment of the present invention.

Fig. 15 is a graph showing experimental results of wettability measurements performed to confirm the effects of the first embodiment of the present invention.

FIG. 16 is a graph showing experimental results of wettability measurements performed to confirm the effect of the first embodiment of the present invention.

Fig. 17 is a graph showing experimental results of wettability measurements performed to confirm the effect of the first embodiment of the present invention.

18 is a cross-sectional view showing the structure of an airtight sealing cover material according to a second embodiment of the present invention.

FIG. 19 is a table showing experimental results of thermal expansion coefficient measurement performed to confirm the effect of the second embodiment of the present invention.

Fig. 20 is a graph showing experimental results of thermal expansion coefficient measurement performed to confirm the effect of the second embodiment of the present invention.

Fig. 21 is a graph showing experimental results of thermal expansion coefficient measurement performed to confirm the effect of the second embodiment of the present invention.

Detailed ways

Hereinafter, embodiments embodying the present invention will be described based on the drawings.

(first embodiment)

First, the structure of the airtight sealing cover material 1 according to the first embodiment of the present invention will be described with reference to FIGS. 1 and 2 .

As shown in FIG. 1 , the hermetic sealing cover material 1 according to the first embodiment is composed of a cover 10 and a glass layer 11 formed on the upper surface 10 a of the cover 10 (on the surface on the Z1 side). The cover 10 is a cuboid having a length L1 of about 2.4 mm in the X direction, a length L2 of about 1.9 mm in the Y direction, and a thickness t1 of about 0.1 mm in the Z direction. Among them, the glass layer 11 is an example of the "bonding layer" of the present invention.

The glass layer 11 is formed to have a substantially uniform width W (see FIG. 2 ) along the end portion of the upper surface 10 a of the cover 10 , and has a thickness t2 of about 0.05 mm in the Z direction. The glass layer 11 is formed in a frame shape along the end portion of the upper surface 10 a of the cover 10 so as to correspond to the upper surface 32 a (see FIG. 4 ) of the frame body 32 of the electronic component housing member 30 described later.

In addition, the glass layer 11 is made of a Pb-free V-based low-melting glass composed of V ₂ O ₅ -P ₂ O ₅ -TeO—Fe ₂ O ₃ . The thermal expansion coefficient α1 of the V-based low-melting glass constituting the glass layer 11 is about 70×10 ^-7 /°C in a temperature range of about 30°C to about 250°C. In addition, the V-based low-melting glass is constituted so that the glass transition temperature is about 285°C. In addition, the glass transition temperature is the temperature at which the thermal expansion coefficient of the V-based low-melting point glass changes rapidly, and the thermal expansion coefficient (about 140×10 ^-7 /°C) in the temperature range above the glass transition temperature is larger than that below the glass transition temperature. Thermal expansion coefficient α1 (approximately 70×10 ^-7 /°C) in the temperature range. In addition, the sealing temperature of the V-based low-melting glass constituting the glass layer 11 is configured to be about 370°C or higher and about 400°C or lower.

In addition, the V-based low-melting-point glass constituting the glass layer 11 is configured to suppress intrusion of water molecules into the interior of the crystal structure. Thereby, the glass layer 11 has moisture resistance (water resistance).

As shown in FIG. 2 , the cover 10 is composed of a metal base 12 and an oxide film layer 13 formed to surround substantially the entire surface of the metal base 12 . The glass layer 11 is formed on the upper surface of the oxide film layer 13 . In addition, the metal base 12 is composed of an Fe-based alloy (42Ni-(2-6)Cr-Fe alloy) containing about 42 mass % Ni, about 2 mass % to about 6 mass % Cr, and Fe. In addition, the metal base material 12 is preferably composed of an Fe-based alloy (42Ni-(3-6)Cr-Fe alloy) containing about 3% by mass or more and about 6% by mass or less of Cr. Among them, the oxide film layer 13 is an example of the "coating layer" in the present invention.

Here, in the first embodiment, the thermal expansion coefficient α2 of the Fe-based alloy constituting the metal substrate 12 is preferably about 55×10 ⁻⁷ /°C or more and about 75×10 ^{− 7} / ℃ below. That is, in the temperature range of about 30°C to about 250°C, the thermal expansion coefficient α1 of the glass layer 11 and the thermal expansion coefficient α2 of the metal substrate 12 preferably satisfy -15×10 ^-7 ≤α2-α1≤5×10 ^-7 Relationship. As a result, in the temperature range of about 30° C. to about 250° C., the glass layer 11 and the metal base 12 are configured to be less prone to stress due to differences in thermal expansion.

In addition, in the first embodiment, the oxide film layer 13 is mainly composed of a Cr ₂ O ₃ film, and has a thickness t3 of about 0.3 μm or more and about 1.2 μm or less in the Z direction. In addition, the oxide film layer 13 is formed by oxidizing Cr contained in the Fe-based alloy of the metal base material 12 on the surface of the metal base material 12 .

Next, the structure of the electronic component storage container 100 using the hermetic sealing lid|cover material 1 which concerns on 1st Embodiment of this invention is demonstrated, referring FIG.3 and FIG.4.

As shown in FIGS. 3 and 4 , the electronic component storage container 100 according to the first embodiment has an electronic component storage member 30 that houses the crystal vibrator 20 (see FIG. 4 ) and a glass layer covered by the above-mentioned hermetically sealed lid material 1 . 11 sealed structure. At this time, the airtight sealing cover material 1 is arranged such that the upper surface 10 a of the cover 10 of the airtight sealing cover material 1 is on the lower side (Z3 side). Among them, the crystal resonator 20 is an example of the "electronic component" of the present invention.

The electronic component housing member 30 is made of Al ₂ O ₃ which is a ceramic material, and has a length L3 of about 2.5 mm in the X direction and a length L4 of about 2.0 mm in the Y direction when viewed in plan. In addition, since the electronic component housing member 30 is made of a ceramic material, it has insulating properties. In addition, the thermal expansion coefficient α3 of Al ₂ O ₃ constituting the electronic component housing member 30 is about 65×10 ^-7 /°C in a temperature range of about 30°C to 250°C. That is, in the temperature range of about 30°C to about 250°C, the thermal expansion coefficient α1 (about 70×10 ⁻⁷ /°C) of the glass layer 11 and the thermal expansion coefficient α3 of the electronic component housing member 30 satisfy 0≦α1−α3( = about 5×10 ^-7 /°C) ≤ 10×10 ^-7 relationship. As a result, the glass layer 11 and the electronic component housing member 30 are configured so that stress due to differences in thermal expansion is less likely to occur in a temperature range of about 30°C to about 250°C.

In addition, the electronic component housing member 30 includes, as shown in FIG. 4 , a bottom 31 on the Z3 side and a frame portion 32 formed to extend in the Z4 direction from around the upper surface (surface on the Z4 side) of the bottom 31 . Moreover, the electronic component housing member 30 is surrounded by the bottom part 31 and the frame part 32, and the recessed part 33 is formed. The concave portion 33 is formed to have an opening on the upper side (Z4 side), and the crystal vibrator 20 is mounted on the upper surface (Z4 side surface) of the bottom portion 31 in the concave portion 33 via the protrusion 40, whereby the crystal vibrator 20 is housed in the In the recess 33.

In addition, the lid 10 of the hermetic sealing lid material 1 is bonded to the upper surface 32 a of the housing 32 of the electronic component housing member 30 via the glass layer 11 . Specifically, the melted glass layer 11 of the hermetic sealing cover material 1 is cooled in a state arranged on the upper surface 32a of the frame body 32, whereby the cover 10 of the hermetic sealing cover material 1 and the electronic component housing member 30 engagement. Thus, the electronic component housing container 100 is sealed. Here, the space constituted by the concave portion 33 of the electronic component housing member 30 housing the crystal vibrator 20, the cover 10 of the hermetic sealing cover material 1, and the glass layer 11 is constituted in an airtight state (approximately vacuum state). ). Thereby, it is possible to suppress changes (deterioration) in the vibration characteristics and the like of the crystal resonator 20 .

In addition, the thermal expansion coefficient α2 of the metal base material 12 is determined based on the relationship between the thermal expansion coefficient α3 of the electronic component housing member 30 and the thermal expansion coefficient α1 of the glass layer 11 . That is, since the thermal expansion coefficient α1 of the glass layer 11 is greater than or equal to the thermal expansion coefficient α3 of the electronic component housing member 30 , no stress or a slight tensile stress is applied to the electronic component housing member 30 side of the glass layer 11 . Here, the metal base material 12 is configured such that the thermal expansion coefficient α2 of the metal base material 12 satisfies the relationship of -15×10 ⁻⁷ ≤ α2 − α1 ≤ 5×10 ⁻⁷ . Either no stress is applied to the side or a slight tensile stress is applied. As a result, even when stress is applied to the glass layer 11, tensile stress from both the cover 10 and the electronic component storage member 30 is applied to the glass layer 11 disposed between the cover 10 and the electronic component storage member 30. Therefore, even the glass layer 11 made of V-based low-melting glass that is prone to cracks (cracks) due to tensile stress is less prone to cracks.

Next, a manufacturing process of the electronic component housing container 100 according to the first embodiment will be described with reference to FIGS. 1 to 6 .

First, a metal substrate 12 made of a 42Ni-(2-6)Cr-Fe alloy as shown in FIGS. 1 and 2 is prepared. Next, as shown in FIG. 5, with respect to the metal substrate 12, in a humid hydrogen atmosphere with a dew point of about 30° C., and at a temperature of about 900° C. to about 1150° C., an oxidation treatment is performed for about 30 minutes ( Preferential oxidation of Cr). In addition, the temperature condition is preferably about 1000°C or higher and about 1150°C or lower. At this time, the dew point of hydrogen is about 30° C., therefore, the partial pressure of oxygen in the humid hydrogen atmosphere is lower than the partial pressure capable of oxidizing Fe and Ni, and on the other hand, greater than the partial pressure capable of oxidizing Cr. Accordingly, on the surface of the metal substrate 12, Fe and Ni are not oxidized, and only Cr is preferentially oxidized. As a result, an oxide film layer 13 mainly composed of Cr ₂ O ₃ and having a thickness t3 (see FIG. 2 ) of about 0.3 μm to about 1.2 μm is formed on substantially the entire surface of the metal substrate 12 .

Next, as shown in FIG. 1 and FIG. 2 , along the end of the upper surface of the oxide film layer 13 (upper surface 10 a of the cover 10 ), a V-based low-temperature coating not containing Pb is applied to the upper surface of the oxide film layer 13 . Paste for melting point glass. Then, firing is performed at a temperature of about 410° C., thereby removing the binder in the V-based low-melting glass paste. Thereby, the lid material 1 for airtight sealing in which the glass layer 11 was formed along the edge part of the upper surface 10a of the lid 10 is manufactured.

In addition, as shown in FIG. 4 , an electronic component storage member 30 is prepared in which the crystal vibrator 20 is stored in the concave portion 33 . Then, the hermetic sealing cover material 1 is placed on the electronic component housing member 30 such that the glass layer 11 of the hermetic sealing cover material 1 is positioned on the upper surface 32 a of the frame body 32 of the electronic component housing member 30 . Then, as shown in FIG. 6 , in the state where the airtight sealing lid material 1 is arranged on the electronic component housing member 30 , it is placed in the vacuum furnace 2 , in a vacuum state, and at a temperature of about 370° C. to about 400° C. Under the following temperature conditions, the glass layer 11 was melted.

Afterwards, by cooling the lid material 1 and the electronic component storage member 30 for airtight sealing, as shown in FIG. The upper surface 32a is engaged. Here, from the fixing temperature (about 300° C.) at which the lid 10 of the hermetic sealing lid material 1 starts bonding with the electronic component housing member 30 to the glass transition temperature (about 285° C. °C) temperature range (temperature range above the glass transition temperature), thermal expansion coefficient α2 with the metal substrate 12 (about 55×10 ^-7 /°C or more, about 75×10 ^-7 /°C or less) and electronic component storage The thermal expansion coefficient (about 140×10 ⁻⁷ /° C.) of the glass layer 11 is larger than the thermal expansion coefficient α3 (about 65×10 ⁻⁷ /° C. or less) of the member 30 . However, since the glass layer 11 has fluidity in a temperature range above the glass transition temperature, there will be no disparity between the lid 10 (metal substrate 12 ), the glass layer 11 , and the electronic component housing member 30 due to differences in thermal expansion coefficients. of stress. In addition, in a temperature range below the glass transition temperature (a temperature range of about 30° C. to about 250° C.), the glass layer 11, the cover 10, and the electronic component housing member 30 are configured so that stress due to differences in thermal expansion hardly occurs, so After cooling, the stress accumulated in the lid 10, the glass layer 11, and the electronic component housing member 30 is small.

In addition, by bonding (sealing) in a vacuum state, the space constituted by the concave portion 33 of the electronic component housing member 30 housing the crystal vibrator 20, the cover 10 of the hermetic sealing cover material 1, and the glass layer 11 has a sufficient space. The airtight state (approximately vacuum state). Further, in order to seal the space formed by the recess 33 , the cover 10 and the glass layer 11 in a more reliable airtight state, it is preferable to melt the glass layer 11 at a temperature of about 380° C. or higher for sealing. In addition, by melting and sealing the glass layer 11 under the temperature condition of about 400° C., the influence of heat during sealing on the crystal vibrator 20 can be reduced. In this manner, the hermetically sealed electronic component housing container 100 shown in FIG. 3 is manufactured.

In the first embodiment, as described above, the hermetic sealing cover material 1 includes: the oxide film layer 13 mainly composed of a _Cr2O3 film _formed on the surface of the metal base material 12; A glass layer 11 having a Pb-free V-series low-melting glass composed of V ₂ O ₅ -P ₂ O ₅ -TeO-Fe ₂ O ₃ is formed on the surface. Thus, the Cr ₂ O ₃ film constituting the oxide film layer 13 and the V-based low-melting glass constituting the glass layer 11 can be sufficiently adhered to each other, so that the metal base 12 and the electronic component housing member 30 can be sufficiently bonded. Accordingly, the airtightness of the electronic component housing container 100 can be sufficiently secured by using the Pb-free V-based low-melting glass. In addition, the hermetic sealing cover material 1 includes the metal base material 12 made of 42Ni-(2-6)Cr-Fe alloy, so that the airtightness can be reduced compared with the case where a ceramic material is used for the base material. Since the thickness t1 of the sealing lid material 1 can suppress the enlargement of the electronic component storage container 100 . In addition, the metal base material 12 is made of a 42Ni-(2-6)Cr-Fe alloy, whereby the oxide film layer 13 made of a Cr ₂ O ₃ film can be easily formed on the surface of the metal base material 12 .

In addition, in the first embodiment, as described above, the thermal expansion coefficient α1 of the glass layer 11 and the thermal expansion coefficient α2 of the metal substrate 12 satisfy -15×10 in the temperature range of about 30° C. to about 250° C. ^-7 ≤ α2-α1 ≤ 5×10 ^-7 , so that when the temperature is lowered from the temperature when the metal substrate 12 is bonded to the glass layer 11, it is possible to reduce the occurrence in the glass layer 11 made of V-based low-melting glass. Therefore, the occurrence of cracks (cracks) in the glass layer 11 made of V-based low-melting glass can be suppressed. In addition, by configuring the coefficient of thermal expansion α1 of the glass layer 11 and the coefficient of thermal expansion α2 of the metal substrate 12 to satisfy the relationship of -15×10 ^-7 ≤ α2 - α1, it is possible to prevent cracking from occurring more easily in response to tensile stress than to compressive stress. , it is possible to suppress excessive tensile stress applied to the V-based low-melting glass constituting the glass layer 11 .

In addition, in the first embodiment, as described above, the thickness t3 of the oxide film layer 13 is about 0.3 μm or more and about 1.2 μm or less, so that the thickness t3 of the oxide film layer 13 can be sufficiently ensured, so that the oxide film layer 13 can be formed The coating film of Cr ₂ O ₃ in the layer 13 is reliably adhered to the V-based low-melting glass constituting the glass layer 11 .

In addition, in the first embodiment, as described above, by configuring the metal base material 12 to be made of a 42Ni-(2-6)Cr-Fe alloy, it is possible to reliably form Cr ₂ O on substantially the entire surface of the metal base material 12 . ₃ oxide coating layer 13. In addition, an increase in the thermal expansion coefficient α2 of the metal substrate 12 due to excessive Cr content can be suppressed, and a significant difference between the thermal expansion coefficient α2 of the metal substrate 12 and the thermal expansion coefficient α1 of the glass layer 11 can be suppressed. Accordingly, it is possible to suppress cracks or the like from occurring in the glass layer 11 or the metal base material 12 due to differences in thermal expansion. In addition, by containing 42% by mass of Ni in the metal base material 12, the thermal expansion coefficient α2 of the metal base material 12 can be reduced, whereby the thermal expansion coefficient α2 of the metal base material 12 can be reliably approached by the thermal expansion coefficient of the metal material compared with ordinary metal materials. The thermal expansion coefficient α1 of the glass layer 11 made of small V-series low-melting glass. As a result, it is possible to further suppress cracks and the like from occurring in the glass layer 11 due to differences in thermal expansion.

In addition, in the first embodiment, as described above, the metal base material 12 is constituted by the 42Ni-(2-6) Cr-Fe alloy, and the thermal expansion coefficient α1 of the glass layer 11 and the thermal expansion coefficient α2 of the metal base material 12 are set to be equal to each other. The relationship of -15×10 ^-7 ≦α2-α1≦5×10 ^-7 is reliably satisfied, and therefore, the occurrence of cracks in the glass layer 11 made of V-based low-melting glass can be reliably suppressed.

In addition, in the first embodiment, as described above, the oxide film layer 13 is formed by surrounding substantially the entire surface of the metal base material 12, which is different from forming the oxide film layer on only one of both surfaces of the metal base material 12. 13, it is possible to prevent the glass layer 11 from being erroneously formed on the surface of the metal substrate 12 on which the oxide film layer 13 is not formed. In addition, unlike the case where the oxide film layer 13 is formed only on a part of the metal base material 12 , it is not necessary to mask a part of the metal base material 12 when forming the oxide film layer 13 . Thereby, the oxide film layer 13 can be easily formed. Furthermore, since the oxide film layer 13 made of corrosion-resistant Cr ₂ O ₃ is formed to surround substantially the entire surface of the metal base 12 , the corrosion resistance of the metal base 12 can be improved.

In addition, in the first embodiment, as described above, the thermal expansion coefficient α1 (about 70×10 ^-7 /°C) of the glass layer 11 and the electronic component housing are controlled by the structure in the temperature range of about 30°C to about 250°C. The thermal expansion coefficient α3 (about 65×10 ^-7 /°C) of the member 30 satisfies the relationship of 0≤α1-α3 (=about 5×10 ^-7 )≤10×10 ^-7 , and when the bonding glass layer 11 and the electronic components are housed When the fixing temperature (approximately 300° C.) of the member 30 is lowered, the stress generated in the glass layer 11 made of V-based low-melting glass can be reduced, and therefore, the stress of the glass layer 11 made of V-based low-melting glass can be suppressed. rupture occurs.

In addition, in the first embodiment, as described above, in the temperature range of about 30°C to about 250°C, the thermal expansion coefficient α1 (about 70×10 ⁻⁷ /°C) of the glass layer 11 and the electronic component housing member The thermal expansion coefficient α3 (about 65×10 ^-7 /°C) of 30 is 0 ≤ α1-α3 (= about 5×10 ^-7 ) ≤ 10×10 ^-7 , and the thermal expansion coefficient α1 of the glass layer 11 and the metal substrate 12 The coefficient of thermal expansion α2 (about 55×10 ^-7 /°C to about 75×10 ^-7 /°C) is -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 . Thus, even when stress is applied to the glass layer 11, since the glass layer 11 disposed between the metal base material 12 and the electronic component housing member 30 is subjected to stress from both the metal base material 12 and the electronic component housing member 30 Therefore, unlike the case where tensile stress is applied to the glass layer 11 only from either the metal substrate 12 or the electronic component housing member 30 , it is possible to suppress the occurrence of cracks in the glass layer 11 .

In addition, in the first embodiment, as described above, for the metal substrate 12, in a humid hydrogen atmosphere with a dew point of about 30° C., which is lower than the partial pressure capable of oxidizing Fe and Ni but higher than the partial pressure capable of oxidizing Cr, and at about Under the temperature condition of 1000°C or more and about 1150°C or less, the oxidation treatment (preferential oxidation of Cr) is performed for about 30 minutes, so that only Cr can be easily oxidized preferentially, so that the surface of the metal substrate 12 can be more reliably and fully The thickness of the oxide film layer 13 composed of a Cr ₂ O ₃ film was ensured.

(example)

Next, thermal expansion coefficient measurement and wettability measurement for confirming the effects of the first embodiment will be described with reference to FIG. 2 and FIGS. 7 to 17 .

(Measurement of coefficient of thermal expansion)

In the measurement of the coefficient of thermal expansion described below, as shown in FIG. 7 , as Examples 1 to 5 corresponding to the metal substrate 12 of the above-mentioned first embodiment, an Fe-based alloy containing 42% by mass of Ni and Fe was used. Fe-based alloys with different Cr contents.

Specifically, as Example 1, an Fe-based alloy (42Ni-2Cr-Fe alloy) containing 2% by mass of Cr was used. In addition, as Example 2, an Fe-based alloy (42Ni-3Cr-Fe alloy) containing 3% by mass of Cr was used. In addition, as Example 3, an Fe-based alloy (42Ni-4Cr-Fe alloy) containing 4% by mass of Cr was used. In addition, as Example 4, an Fe-based alloy (42Ni-5Cr-Fe alloy) containing 5% by mass of Cr was used. In addition, as Example 5, an Fe-based alloy (42Ni-6Cr-Fe alloy) containing 6% by mass of Cr was used.

On the other hand, as Comparative Example 1 with respect to Examples 1 to 5, an Fe-based alloy (42Ni—Fe alloy) containing 42% by mass of Ni and Fe and not containing Cr was used. In addition, as Reference Example 1 for the metal base material of the first embodiment, glass layer 11 composed of V ₂ O ₅ -P ₂ O ₅ -TeO-Fe ₂ O ₃ constituting the glass layer 11 of the first embodiment described above was used. Pb-based V-series low-melting glass. In addition, as Reference Example 2, Al ₂ O ₃ constituting the electronic component housing member 30 of the above-mentioned first embodiment was used.

Furthermore, by changing the temperature of each member in Examples 1 to 5, Comparative Example 1, and Reference Examples 1 and 2, the elongation of each member was measured. Here, the elongation refers to the value obtained by dividing the elongation of the member at any temperature (the amount obtained by subtracting the reference length at room temperature (30°C) from the length at any temperature) by the reference length at room temperature . The slope of the straight line connecting the elongation at room temperature and the elongation at 250°C was obtained as the coefficient of thermal expansion in the temperature range of 30°C to 250°C.

As shown in FIG. 8 , as an experimental result of elongation measurement, by adding Cr to the 42Ni—Fe alloy (Comparative Example 1), the elongation (thermal expansion coefficient) can be increased. In addition, elongation can be increased by increasing the amount of Cr added.

In addition, in the temperature range below the glass transition temperature (285°C) of the V-series low-melting glass, the elongation of the 42Ni-Fe alloy of Comparative Example 1 was higher than that of the V-series low-melting glass (Reference Example 1). The rate is much smaller. In addition, the elongation of the 42Ni-2Cr-Fe alloy of Example 1 was also smaller than that of the V-based low-melting glass (Reference Example 1). On the other hand, the elongation of the alloys of 42Ni-(3-6)Cr-Fe in Examples 2 to 5 were values close to the elongation of the V-based low-melting glass (Reference Example 1).

In addition, as shown in Fig. 7 and Fig. 9, as the thermal expansion coefficient, the thermal expansion coefficient α1 of the V-based low-melting glass (Reference Example 1) is 72×10 ^-7 /°C in the temperature range of 30°C to 250°C, The thermal expansion coefficient α3 of Al ₂ O ₃ (Reference Example 2) was 65×10 ^-7 /°C. As a result, it was confirmed that the thermal expansion coefficient α1 of V-based low-melting glass (Reference Example 1) and the thermal expansion coefficient α3 of Al ₂ O ₃ (Reference Example 2) satisfy 0≤α1-α3 (=7×10 ^-7 )≤10× 10 ^-7 relationship.

In addition, it was confirmed that in the temperature range of 30°C to 250°C, the thermal expansion coefficient α2 of the 42Ni-Fe alloy of Comparative Example 1 is 40×10 ^-7 /°C, which is higher than the thermal expansion of the V-based low-melting glass (Reference Example 1). The coefficient α1 (72×10 ^-7 /°C) is only 32×10 ^-7 /°C smaller. That is, when the metal substrate of Comparative Example 1 composed of 42Ni-Fe alloy is bonded to V-series low-melting glass at the sealing temperature (about 370°C to about 400°C), the difference in thermal expansion coefficient (α2-α1) is large (- 32×10 ^-7 /°C), therefore, it is considered that cracks (cracks) are likely to occur in the glass layer made of v-based low-melting glass during cooling.

In addition, it was confirmed that in the temperature range of 30°C to 250°C, the thermal expansion coefficient α2 of the 42Ni-2Cr-Fe alloy of Example 1 is 56×10 ^-7 /°C, which is lower than that of the V-based low-melting glass (Reference Example 1). The thermal expansion coefficient α1 (72×10 ^-7 /°C) is only 16×10 ^-7 /°C smaller. That is, when the metal substrate of Example 1 composed of 42Ni-2Cr-Fe alloy and the V-based low-melting glass are bonded at the sealing temperature, the difference in thermal expansion coefficient is to some extent (-16×10 ^-7 /°C), Therefore, it is considered that cracks may occur in the glass layer made of V-based low-melting glass during cooling.

On the other hand, it was confirmed that the thermal expansion coefficient α2 of the 42Ni-(3-6)Cr-Fe alloys of Examples 2 to 5 was 62×10 ^-7 /°C to 74× Below 10 ^-7 /°C, it satisfies the relationship of -10×10 ^-7 ≤α2-α1≤2×10 ^-7 with the thermal expansion coefficient α1 (72×10 ^-7 /°C) of V-series low-melting glass (Reference Example 1) . That is, when the metal substrates of Examples 2 to 5 composed of 42Ni-(3-6)Cr-Fe alloys and the V-series low-melting glass are bonded at the sealing temperature, there is not much difference in thermal expansion coefficient, so it is considered that it is possible to suppress Cracks occur in the glass layer made of V-based low-melting glass during cooling. As a result, it is considered that 42Ni-(3-6)Cr-Fe alloy is preferable as the metal base material.

(wettability determination)

In the wettability measurement described below, 42Ni-4Cr-Fe alloy was used as Examples 6 to 9 corresponding to the metal substrate 12 of the above-mentioned first embodiment, and 42Ni-6Cr-Fe alloy was used as Examples 10 to 13. Fe alloy. In addition, in Examples 6 to 9, the temperature conditions at the time of preferential oxidation of Cr are different, and in Examples 10 to 13, the temperature conditions at the time of preferential oxidation of Cr are different. Among them, the preferential oxidation of Cr was carried out in a humid hydrogen atmosphere with a dew point of 30° C. for 30 minutes.

Specifically, as shown in FIG. 10 and FIG. 11 , as Examples 6 and 10, Cr was preferentially oxidized under the temperature condition of 900°C. In addition, as Examples 7 and 11, the preferential oxidation of Cr was carried out under the temperature condition of 1000°C. In addition, as Examples 8 and 12, Cr was preferentially oxidized under the temperature condition of 1100°C. In addition, as Examples 9 and 13, the preferential oxidation of Cr was carried out under the temperature condition of 1150°C.

Then, the thickness t3 of the oxide film layer composed of Cr ₂ O ₃ formed on the surface of the 42Ni-4(6)Cr—Fe alloys of Examples 6 to 13 was measured (see FIG. 2 ).

In addition, as shown in FIG. 12 , paste 114 of V-based low-melting glass was applied to the surface of cover 110 composed of metal substrate 112 and oxide film layer 113 in Examples 6, 8 to 10, 12 and 13. Similarly, paste 114 of V-based low-melting glass was applied to the surface of cover 110 made of Al ₂ O ₃ (Reference Example 2). At this time, three pastes 114 having different widths W are applied on the surface of the cover 110 . Specifically, the paste 114a having a width W1 of 290 μm, the paste 114b having a width W2 of 400 μm, and the paste 114c having a width W3 of 460 μm were applied to the surface of the cover 110 . At this time, the thickness t4 of the pastes 114a, 114b, and 114c is all applied to be 80 μm.

Then, firing is performed at a temperature of 410°C to remove the binder in the pastes 114a, 114b, and 114c. Thereby, as shown in FIG. 13, paste 114a, 114b, 114c (refer FIG. 12) becomes glass layer 111a, 111b, 111c, respectively. Thereafter, the width W1a and thickness t4a of the glass layer 111a, the width W2a and thickness t4b of the glass layer 111b, and the width W3a and thickness t4c of the glass layer 111c are respectively measured. Then, the rate of change of the width and thickness of the glass layer 111 a ( 111 b and 111 c ) with respect to the width and thickness of the paste 114 a ( 114 b and 114 c ) were respectively obtained. At this time, when the width (thickness) of the glass layer 111 is larger than the width (thickness) of the paste 114, the rate of change is set to a positive value, and when the width (thickness) of the glass layer 111 is smaller than the width (thickness) of the paste 114 , the rate of change is set to a negative value.

As shown in FIG. 10 , in the 42Ni-4Cr-Fe alloy, the thickness t3 of the oxide film layer in Example 6 (900° C.) was less than 0.1 μm. That is, it is considered that the oxide film was not formed to a sufficient thickness in Example 6 (900° C.). On the other hand, in Examples 7 to 9 (1000°C, 1100°C, 1150°C), the thickness t3 of the oxide film layer was 0.3 μm or more. In addition, as shown in FIG. 11, in any of Examples 10 to 13 (900°C, 1000°C, 1100°C, and 1150°C) in the 42Ni-6Cr-Fe alloy, the thickness t3 of the oxide film layer was 0.3 μm or more. .

In addition, in Example 6 (4Cr) and Example 10 (6Cr) where the temperature condition is 900°C, Example 7 (4Cr) and Example 11 (6Cr) where the temperature condition is 1000°C, and the temperature condition is 1100°C. In any of Example 8 (4Cr) and Example 12 (6Cr), and Example 9 (4Cr) and Example 13 (6Cr) at a temperature of 1150°C, Examples 10 to 13 using 42Ni-6Cr-Fe alloy The thickness t3 of the oxide film layer is larger than the thickness t3 of the oxide film layer in Examples 6 to 9 using the 42Ni-4Cr-Fe alloy. From this, it became clear that increasing the Cr content can increase the thickness t3 of the oxide film layer under the same temperature conditions.

In addition, as shown in FIG. 14 and FIG. 16 , it was confirmed that the rate of change in the width of Examples 6 and 10 (900° C.) was less than −40% in all the glass layers 111 a , 111 b , and 111 c . In addition, as shown in FIG. 15 and FIG. 17 , the rate of change in thickness in Examples 6 and 10 was 0% or more except for the thickness (−2%) of the glass layer 111 a in Example 6. This is because in Examples 6 and 10, the oxide film layer was insufficient or incompletely formed, so the wettability was low, and the V-based low-melting glass and the oxide film layer were in a state of insufficient adhesion. Therefore, it is considered that many parts of the glass layer 111 that spread in the width direction are raised in the thickness direction.

On the other hand, as shown in Fig. 14 and Fig. 16, the rate of change of the width in Examples 8 and 12 (1100°C), Examples 9 and 13 (1150°C) and Reference Example 2 (Al ₂ O ₃ ), in All the glass layers 111a, 111b, and 111c are -30% or more. In addition, as shown in FIG. 15 and FIG. 17 , the rate of change in thickness in Examples 8 and 12, Examples 9 and 13, and Reference Example 2 was less than -10% in all glass layers 111a, 111b, and 111c. As a result, in Examples 8 and 12, and Examples 9 and 13, since the oxide film layer was sufficiently formed, the wettability was high, and the V-based low-melting glass and the oxide film layer were in a sufficiently adhered state. This prevents the portion of the glass layer 111 that spreads in the width direction from moving in the thickness direction, prevents it from swelling in the thickness direction, and reduces the volume of the adhesive in the width and thickness directions.

That is, it was confirmed that the preferential oxidation of Cr proceeds in the temperature range of 1000° C. or higher, and the V-based low-melting glass and the oxide film layer can be brought into a state of sufficient adhesion, which is preferable. On the other hand, preferential oxidation of Cr in a temperature range exceeding 1150°C requires equipment with high heat resistance, so it is considered more preferable to perform preferential oxidation of Cr in a temperature range of 1000°C to 1150°C.

In addition, compared with Examples 8 and 12 (1100°C), the rate of change in width and the rate of change in thickness in Examples 9 and 13 (1150°C) are less overall, so it is considered that the temperature at 1150°C is more preferable. The preferential oxidation of Cr is carried out under the temperature conditions.

(Second Embodiment)

Next, a second embodiment of the present invention will be described with reference to FIG. 18 . The hermetic sealing lid material 201 of this second embodiment differs from the above-mentioned first embodiment in that the case where the metal base material 212 is made of a three-layer composite material will be described.

The metal substrate 212 of the cover 210 in the hermetic sealing cover material 201 according to the second embodiment of the present invention is arranged on the first layer 212 a arranged on the side of the glass layer 11 (Z1 side), as shown in FIG. 18 . The second layer 212b on the Z2 side (opposite side to the glass layer 11 ) of the first layer 212a is bonded to the third layer 212c arranged on the Z2 side (opposite side to the glass layer 11 ) of the second layer 212b . So-called 3-layer composite construction. In addition, both the first layer 212a and the third layer 212c are composed of a common Fe-based alloy (42Ni-6Cr-Fe) containing about 42% by mass of Ni, about 6% by mass of Cr, and Fe. In addition, the second layer 212 b is made of a common Fe-based alloy (42Ni—Fe) containing about 42% by mass of Ni and Fe.

In addition, the thermal expansion coefficient α4 of the 42Ni-6Cr-Fe alloy constituting the first layer 212a and the third layer 212c is about 75×10 ^-7 /°C. In addition, the thermal expansion coefficient α5 of the 42Ni-Fe alloy constituting the second layer 212b is about 40×10 ⁻⁷ /°C. That is, the coefficient of thermal expansion α4 (about 75×10 ⁻⁷ /°C) of the first layer 212 a and the third layer 212 c is greater than the coefficient of thermal expansion α1 (about 70×10 ⁻⁷ /° C.) of the glass layer 11 , and the coefficient of thermal expansion of the second layer 212 b The thermal expansion coefficient α5 (about 40×10 ⁻⁷ /° C.) is smaller than the thermal expansion coefficient α1 of the glass layer 11 .

Here, in the second embodiment, the total thickness (thickness of the cover 210 ) t1 of the first layer 212 a , the second layer 212 b , and the third layer 212 c is about 0.1 mm. In addition, the first layer 212a and the third layer 212c have the same thickness t5 in the Z direction, and on the other hand, the second layer 212b has a thickness t6 in the Z direction. Here, the thickness t5 is preferably about 50% or more of the thickness t6. That is, the total thickness (2×t5 ) of the first layer 212 a and the third layer 212 c is preferably about 50% or more (about 0.05 mm or more) of the thickness t1 (=2×t5+t6 ) of the cover 210 . As a result, the thermal expansion coefficient α2 of the composite material constituting the metal substrate 212 is configured to be about 55×10 ^-7 /°C to about 75×10 ^-7 /°C in a temperature range of about 30°C to about 250°C. . That is, in the temperature range of about 30°C to about 250°C, the composite of the thermal expansion coefficient α1 (about 70×10 ^-7 /°C) of the V-based low-melting glass constituting the glass layer 11 and the metal base material 212 The thermal expansion coefficient α2 of the material satisfies the relationship of -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 .

In addition, an oxide film layer 213a mainly composed of _Cr2O3 is formed on the Z1 side surface and side surface of the first layer 212a, and an oxide film layer 213a mainly composed of _Cr2O3 is formed on the Z2 side surface and side surface of the third layer _212c . ₃ composed of oxide film layer 213b. The oxide film layers 213a and 213b pass through the surface and side surface of the Z1 side of the first layer 212a and the Z2 side of the third layer 212c through the Cr contained in the 42Ni-6Cr-Fe alloy of the first layer 212a and the third layer 212c, respectively. Formed by oxidation of the side faces and sides. In addition, other configurations of the second embodiment are the same as those of the above-mentioned first embodiment.

Next, with reference to FIG. 18 , the manufacturing process of the hermetic sealing cover material 201 according to the second embodiment of the present invention will be described.

First, a sheet material (not shown) made of a 42Ni—Fe alloy having a predetermined thickness is prepared. In addition, two plates made of 42Ni-6Cr-Fe alloy and having a thickness of about 50% or more of the thickness of the plate member made of 42Ni-Fe alloy were prepared. Then, in the state where the plate made of 42Ni-Fe alloy is sandwiched by the plate made of 42Ni-6Cr-Fe alloy, the plate made of 42Ni-Fe alloy and the pair of plates made of 42Ni-6Cr-Fe alloy Joining is performed while applying a predetermined pressure. Thus, as shown in FIG. 18, the first layer 212a composed of 42Ni-6Cr-Fe alloy, the second layer 212b composed of 42Ni-Fe alloy, and the third layer 212c composed of 42Ni-6Cr-Fe alloy are sequentially formed. They are bonded in a stacked state to form a three-layer composite material. At this time, the thickness t5 of the first layer 212a and the third layer 212c are both about 50% or more of the thickness t6 of the second layer 212b. Thereafter, the metal base material 211 is formed by cutting the composite material into a predetermined shape.

Then, under the same conditions as in the above-mentioned first embodiment, Cr is preferentially oxidized, thereby forming an oxide film layer _213a mainly composed of _Cr2O3 on the Z1-side surface and side surface of the first layer 212a, and An oxide film layer 213b mainly composed of Cr ₂ O ₃ is formed on the Z2-side surface and side surface of the third layer 212c. In addition, other manufacturing processes of the second embodiment of the present invention are the same as those of the first embodiment.

In the second embodiment, as described above, the hermetic sealing cover material 201 includes: the oxide film layers 213a and 213b mainly composed of Cr ₂ O ₃ films formed on the surface of the metal base 212; The glass layer 11 made of Pb-free V-series low-melting glass is formed on the surface of the layer 213 a , so that the metal base 212 and the electronic component housing member 30 (see FIG. 4 ) can be sufficiently bonded. In addition, the hermetic sealing lid material 201 has a metal base material 212 made of a 42Ni-6Cr-Fe alloy, so that the thickness of the hermetic sealing lid material 201 can be reduced compared to the case where a ceramic material is used as the base material. t1. Furthermore, since metal base 212 contains 42Ni-6Cr-Fe alloy, oxide film layers 213a and 213b made of Cr ₂ O ₃ films can be easily formed on the surface of metal base 212 .

In addition, in the second embodiment, as described above, the metal base 212 is composed of the first layer 212a, the second layer 212b arranged on the Z2 side of the first layer 212a, and the third layer 212b arranged on the Z2 side of the second layer 212b. The layer 212c is formed by bonding the formed 3-layer composite material, and the first layer 212a and the third layer 212c are composed of 42Ni-6Cr-Fe alloy, and the second layer 212b is composed of 42Ni-Fe alloy, thereby, it is compatible with the metal substrate 212 Compared with the case of only one layer, the thermal expansion coefficient α2 of the metal base 212 can be easily adjusted by joining different types of metal materials having different thermal expansion coefficients. In addition, the first layer 212a and the third layer 212c made of 42Ni-6Cr-Fe alloy can be disposed on both surfaces of the hermetic sealing cover material 201, therefore, on both surfaces of the metal base 212 (the first layer 212a Oxide film layers 213a and 213b made of Cr ₂ O ₃ films can be formed on the surfaces on the Z1 side of the third layer 212c and the Z2 side surface of the third layer 212c. This prevents glass layer 11 from being erroneously formed on the surface of metal base 212 on which no oxide layer is formed, unlike the case where the oxide layer is formed only on either surface of metal base 212 .

In addition, in the second embodiment, as described above, the first layer 212a, the second layer 212b, and the third layer 212c of the metal base 212 are composed of an Fe-based alloy containing 42% by mass of Ni. The coefficients of thermal expansion of the first layer 212a, the second layer 212b, and the third layer 212c are all reduced. Accordingly, the thermal expansion coefficient α2 of the metal substrate 212 can be reliably brought close to the thermal expansion coefficient α1 of the glass layer 11 made of V-based low-melting glass having a thermal expansion coefficient smaller than that of ordinary metal materials. In addition, if the first layer 212a and the third layer 212c are composed of a general 42Ni-6Cr-Fe alloy, and the second layer 212b is composed of a general 42Ni-Fe alloy, then it is possible to use an easily available Fe-based alloy, corresponding to the formation On the surface of the metal base material 212 in _the region of the glass layer 11, oxide film layers 213a and 213b made of _Cr2O3 films are formed, and the thermal expansion coefficient α2 of the metal base material 212 is made close to glass made of V-based low-melting point glass. The coefficient of thermal expansion α1 of layer 11 .

In addition, in the second embodiment, as described above, the thermal expansion coefficient α4 (approximately 75×10 ⁻⁷ /°C) of the first layer 212 a and the third layer 212 c is configured to be larger than the thermal expansion coefficient α1 (approximately 70×10 ^-7 /°C), and the thermal expansion coefficient α5 (about 40×10 ^-7 /°C) of the second layer 212b is smaller than the thermal expansion coefficient α1 of the glass layer 11, thus, by adjusting the thickness t5 of the first layer 212a, the second layer The thickness t6 of the 212b and the thickness t5 of the third layer 212c can make the thermal expansion coefficient α2 of the metal substrate 212 as a whole approach the thermal expansion coefficient α1 of the glass layer 11 .

In addition, in the second embodiment, as described above, the total thickness (2×t5) of the first layer 212 a and the third layer 212 c is about 50% or more of the thickness t1 (=2×t5+t6) of the cover 210 . Therefore, the thermal expansion coefficient α1 of the glass layer 11 and the thermal expansion coefficient α2 of the metal substrate 212 can satisfy the relationship of -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 . Cracks (cracks) occur in the glass layer 11 made of fusing glass. In addition, other effects of the second embodiment are the same as those of the first embodiment described above.

(example)

Next, the measurement of the coefficient of thermal expansion to confirm the effect of the second embodiment will be described with reference to FIGS. 18 to 21 .

(Measurement of coefficient of thermal expansion)

In the measurement of the coefficient of thermal expansion described below, as shown in FIG. 19 , as Examples 14 to 18 corresponding to the metal substrate 212 of the above-mentioned second embodiment, a first layer 212a made of a 42Ni-6Cr-Fe alloy, A 3-layer composite material of the second layer 212b made of 42Ni-Fe alloy and the third layer 212c made of 42Ni-6Cr-Fe alloy, and the total thickness of the first layer 212a and the thickness of the third layer 212c (2× The ratio (thickness ratio) of t5 (see FIG. 18 )) to the thickness t1 of the cover 210 is different.

Specifically, as Example 14, the total thickness (2×t5) of the first layer 212a and the third layer 212c is set to 12.5% of the thickness t1 of the cover 210, and the thickness t6 of the second layer 212b (see FIG. 18) Set to 87.5% of the thickness t1 of the cover 210 . In addition, as Example 15, the total thickness (2×t5) was set to 25% of the thickness t1, and the thickness t6 was set to 75% of the thickness t1. In addition, as Example 16, the total thickness (2×t5) was set to 50% of the thickness t1, and the thickness t6 was set to 50% of the thickness t1. In addition, as Example 17, the total thickness (2×t5) was set to 67% of the thickness t1, and the thickness t6 was set to 33% of the thickness t1. In addition, as Example 18, the total thickness (2×t5) was set to 75% of the thickness t1, and the thickness t6 was set to 25% of the thickness t1.

In addition, as Comparative Example 1 with respect to Examples 14 to 18, the same metal substrate composed of only 42Ni—Fe alloy as in Comparative Example 1 of the above-mentioned first embodiment was used. That is, as Comparative Example 1, a metal substrate in which the thickness ratio of the thickness t5 of the 42Ni-6Cr-Fe alloy was 0% was used. In addition, as Comparative Example 3, the same metal substrate composed of only 42Ni-6Cr-Fe alloy as in Example 5 of the above-mentioned first embodiment was used. That is, as Comparative Example 3, a metal base material in which the thickness ratio of the thickness t5 of the 42Ni-6Cr-Fe alloy was 100% was used. In addition, as in the first embodiment, V-based low-melting glass was used as Reference Example 1, and Al ₂ O ₃ was used as Reference Example 2.

In addition, the elongation of each member of Examples 14 to 18, Comparative Examples 1 and 3, and Reference Examples 1 and 2, and the 250° C. The coefficient of thermal expansion for the temperature range below °C.

As shown in FIG. 20 , as an experimental result of elongation measurement, the elongation (thermal expansion coefficient) can be increased by increasing the sheet thickness ratio of the 42Ni-6Cr-Fe alloy.

In addition, in the temperature range below the glass transition temperature (285°C) of the V-series low-melting glass, the elongation of Example 14 (12.5%) and Example 15 (25%) is smaller than that of the V-series low-melting glass (reference Example 1) elongation. On the other hand, the elongation percentages of Examples 16 to 18 and Comparative Example 3 (50% to 100%) are values close to the elongation percentages of the V-based low-melting glass (Reference Example 1).

In addition, as shown in FIG. 19 and FIG. 21 , it was confirmed that the thermal expansion coefficient α2 of Example 14 (12.5%) was 45×10 ^-7 /°C in the temperature range of 30°C to 250°C as the thermal expansion coefficient. The thermal expansion coefficient α1 (72×10 ^-7 /°C) of the V-series low-melting glass (Reference Example 1) is only 27×10 ^-7 /°C smaller. In addition, it was confirmed that the thermal expansion coefficient α2 of Example 15 (25%) is 51×10 ^-7 /°C, which is only smaller than the thermal expansion coefficient α1 (72×10 ^-7 /°C) of the V-based low-melting glass (Reference Example 1) 21×10 ^-7 /°C. That is, the difference in thermal expansion coefficient (α2 -α1) is large to a certain extent (-27(21)×10 ^-7 /°C), so it is considered that cracks (cracks) may occur in the glass layer made of V-based low-melting glass during cooling.

On the other hand, it was confirmed that the thermal expansion coefficient α2 of Examples 16 to 18 and Comparative Example 3 (50% to 100%) in the temperature range of 30°C to 250°C was 58×10 ^-7 /°C to 74×10 Below ^-7 /°C, and the thermal expansion coefficient α1 (72×10 ^-7 /°C) of the V-series low-melting glass (Reference Example 1), satisfy the relationship of -14×10 ^-7 ≤ α2-α1 ≤ 2×10 ^-7 . That is, when the metal substrates of Examples 16 to 18 are bonded to the V-series low-melting glass at the sealing temperature, there is almost no difference in thermal expansion coefficient, so it is considered that it is possible to suppress the generation of a glass layer made of the V-series low-melting glass during cooling. rupture. As a result, as the metal base material, it is considered preferable to set the plate thickness ratio of the 42Ni-6Cr-Fe alloy to 50% or more of the metal base material (cover).

In addition, it should be understood that embodiment and the Example disclosed this time are an illustration and a limitation. The scope of the present invention is shown not by the description of the above-mentioned embodiment and examples but by the scope of the claims, and includes all changes within the meaning and range equivalent to the scope of the claims.

For example, in the above-mentioned first embodiment, the metal base material 12 shows an example composed of 42Ni-(2-6)Cr-Fe alloy, and in the above-mentioned second embodiment, it shows that the metal base material 212 is made of 42Ni-6Cr - An example of a composite material composed of a first layer 212a made of an Fe alloy, a second layer 212b made of a 42Ni-Fe alloy, and a third layer 212c made of a 42Ni-6Cr-Fe alloy, but the present invention is not limited thereto . The metal material constituting the metal base material of the present invention does not necessarily need to contain Ni, but may contain Cr.

In addition, in the above-mentioned first and second embodiments, examples were shown in which the oxide film layers 13 ( 213 a and 213 b ) mainly composed of Cr ₂ O ₃ films were formed in addition to the portion where the glass layer 11 was arranged, but the present invention does not limited to this. In the present invention, the oxide film layer can be formed only in the portion where the glass layer is arranged.

In addition, in the above-mentioned second embodiment, an example was shown in which the metal base 212 is composed of a three-layer composite material obtained by bonding the first layer 212a, the second layer 212b, and the third layer 212c, but the present invention is not limited thereto. For example, it may be composed of a two-layer composite material in which a first layer made of a 42Ni-6Cr-Fe alloy is bonded to a second layer made of a 42Ni-Fe alloy. In addition, it may be composed of a composite material obtained by bonding four or more layers.

In addition, in the second embodiment described above, an example was shown in which the first layer 212a and the third layer 212c were composed of 42Ni-6Cr-Fe alloys having the same composition, but the present invention is not limited thereto. In the present invention, the composition of the first layer 212a and the composition of the third layer 212c may be different. In this case, the Cr content of the first layer 212 a arranged on the side of the glass layer 11 is preferably about 3% by mass or more.

In addition, in the above-mentioned first and second embodiments, the example in which the glass layer 11 is made of V ₂ O ₅ -P ₂ O ₅ -TeO-Fe ₂ O ₃ and does not contain Pb is shown. The invention is not limited thereto. In the present invention, the glass layer may be a Pb-free glass material other than V-based low-melting glass. At this time, by using a glass material that melts at a temperature of about 400° C. or lower, the influence of heat during sealing on the crystal resonator can be reduced.

In addition, in the above-mentioned first and second embodiments, an example in which the crystal vibrator 20 is housed in the container 100 for housing electronic components is shown, but the present invention is not limited thereto, and for example, a SAW filter (surface acoustic wave filter) may be housed In a container for storing electronic parts.

Claims (20)

1. A lid material for airtight sealing, characterized in that: It is an airtight sealing cover material (1, 201) used in an electronic component storage container (100) including an electronic component storage member (30) made of a ceramic material for storing electronic components (20), have: a metal substrate (12, 212) comprising a metallic material containing at least Cr; a coating layer (13, 213a, 213b) formed of a Cr oxide film formed on the surface of the metal substrate; and A bonding layer (11) formed on the surface of the cladding layer and made of a Pb-free glass material for bonding the metal substrate on which the cladding layer is formed and the electronic component housing member. . 2. The lid material for airtight sealing as claimed in claim 1, characterized in that: In the temperature range of 30°C to 250°C, the thermal expansion coefficient α1(/°C) of the joining layer and the thermal expansion coefficient α2(/°C) of the metal substrate satisfy -15×10 ^-7 ≤α2-α1≤ 5×10 ^-7 relationship. 3. The lid material for airtight sealing as claimed in claim 1, characterized in that: The coating layer has a thickness of 0.3 μm or more. 4. The lid material for airtight sealing as claimed in claim 1, characterized in that: The metal base material includes an Fe-based alloy containing Ni, 3% by mass to 6% by mass of Cr, and Fe. 5. The lid material for airtight sealing as claimed in claim 4, characterized in that: The metal base material is composed of an Fe-based alloy containing 42 mass % of Ni, 3 mass % to 6 mass % of Cr, and Fe. 6. The lid material for airtight sealing as claimed in claim 1, characterized in that: The coating layer is formed on the surface of the metal base on which the bonding layer is disposed and on the surface of the metal base on the side opposite to the side on which the bonding layer is disposed. 7. The lid material for airtight sealing as claimed in claim 1, characterized in that: The metal base material is composed of a composite material disposed on the bonding layer side and includes at least a first layer (212a) containing at least Cr and a second layer (212b) containing a metal material different from the first layer. 8. The lid material for airtight sealing as claimed in claim 7, characterized in that: The thermal expansion coefficient of the first layer is greater than the thermal expansion coefficient of the bonding layer, and the thermal expansion coefficient of the second layer is smaller than the thermal expansion coefficient of the bonding layer. 9. The lid material for airtight sealing as claimed in claim 7, characterized in that: The first layer of the metal base material is composed of an Fe-based alloy containing Ni, 3% by mass to 6% by mass of Cr, and Fe. 10. The lid material for airtight sealing as claimed in claim 7, characterized in that: said metal substrate is composed of a composite material comprising said first layer, said second layer and a third layer, the first layer, disposed on the bonding layer side, contains at least Cr; the second layer, disposed on the opposite side of the first layer from the bonding layer, comprises a different metal material from the first layer; The third layer (212c) is disposed on the opposite side of the second layer to the first layer, and contains at least Cr. 11. The lid material for airtight sealing as claimed in claim 10, characterized in that: Both the first layer and the third layer are composed of an Fe-based alloy containing Ni, 3% by mass to 6% by mass of Cr, and Fe. 12. The lid material for airtight sealing as claimed in claim 11, characterized in that: Both the first layer and the third layer are composed of an Fe-based alloy containing 42% by mass of Ni, 6% by mass of Cr, and Fe, The second layer is made of an Fe-based alloy containing 42% by mass of Ni and Fe. 13. The lid material for airtight sealing according to claim 11, characterized in that: The total thickness of the first layer and the third layer is 50% or more of the entire thickness of the metal base material. 14. A container (100) for storing electronic components, characterized in that: A cover material (1, 201) for airtight sealing and an electronic component storage member (30) are provided, wherein, The lid material (1, 201) for airtight sealing includes: a metal base material (12, 212) having a metal material containing at least Cr; an oxide film made of Cr formed on the surface of the metal base material a clad layer (13, 213a, 213b); and a bonding layer (11) formed of a Pb-free glass material formed on a surface of the clad layer; and, The electronic component storage member (30) is bonded to the metal base material on which the cladding layer is formed via the bonding layer, is made of a ceramic material, and is used to store electronic components (20). 15. The container for storing electronic components according to claim 14, characterized in that: In the temperature range of 30°C to 250°C, the thermal expansion coefficient α1(/°C) of the bonding layer and the thermal expansion coefficient α3(/°C) of the electronic component housing member satisfy 0≤α1-α3≤10×10 ^{− 7} relationships. 16. The container for storing electronic components according to claim 15, wherein: In the temperature range of 30°C to 250°C, the thermal expansion coefficient α1(/°C) of the bonding layer and the thermal expansion coefficient α3(/°C) of the electronic component housing member satisfy 0≤α1-α3≤10×10 ^{− 7} , and the coefficient of thermal expansion α1 (/°C) of the bonding layer and the coefficient of thermal expansion α2 (/°C) of the metal substrate satisfy -15×10 ^-7 ≤ α2-α1 ≤ 5×10 ^-7 relation. 17. A method of manufacturing an airtight sealing cover material, characterized in that: It is used for manufacturing an airtight sealing lid material used in an electronic component storage container (100) including an electronic component storage member (30) made of a ceramic material for storing electronic components (20), the manufacturing method comprising : On the surface of a metal substrate (12, 212) containing a metal material containing at least Cr, a coating layer (13, 213a, 213b) composed of a Cr oxide film is formed by oxidizing Cr of the metal substrate process; and A step of forming, on the surface of the cladding layer, a bonding layer (11) made of a Pb-free glass material for joining the metal substrate on which the cladding layer is formed and the electronic component housing member (11). . 18. The method of manufacturing an airtight sealing lid material according to claim 17, characterized in that: The step of forming the coating layer includes the step of forming the coating layer composed of a Cr oxide film on the surface of the metal base material including a metal material having an Fe-based alloy, wherein the The Fe-based alloy contains Ni, 3% by mass to 6% by mass of Cr, and Fe. 19. The method of manufacturing an airtight sealing lid material according to claim 18, characterized in that: The step of forming the coating layer composed of an oxide film of Cr includes: preferentially oxidizing Cr of the metal substrate under a humid hydrogen atmosphere at a temperature of 1000° C. to 1150° C. The step of forming the coating layer composed of a Cr oxide film on the surface of the metal substrate is preferentially performed. 20. The method of manufacturing an airtight sealing lid material according to claim 19, characterized in that: The step of preferentially forming the coating layer composed of an oxide film of Cr includes: under the humid hydrogen atmosphere in which the partial pressure of oxygen is set to be lower than the partial pressure capable of oxidizing Fe and Ni and higher than the partial pressure capable of oxidizing Cr. , a step of preferentially forming the coating layer composed of a Cr oxide film.

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