KR20160052381A - Lid for gas-tight seal and manufacturing method of the same, electronic component receiving package using the same - Google Patents

Lid for gas-tight seal and manufacturing method of the same, electronic component receiving package using the same Download PDF

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KR20160052381A
KR20160052381A KR1020150151176A KR20150151176A KR20160052381A KR 20160052381 A KR20160052381 A KR 20160052381A KR 1020150151176 A KR1020150151176 A KR 1020150151176A KR 20150151176 A KR20150151176 A KR 20150151176A KR 20160052381 A KR20160052381 A KR 20160052381A
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metal layer
layer
edx
sem
oxide film
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KR101799645B1 (en
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신이치로 요코야마
마사아키 이시오
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히타치 긴조쿠 가부시키가이샤
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/3121—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/315—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed the encapsulation having a cavity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3731—Ceramic materials or glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/161—Cap
    • H01L2924/1615—Shape
    • H01L2924/16195—Flat cap [not enclosing an internal cavity]

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Laser Beam Processing (AREA)
  • Glass Compositions (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a lid for gas-tight seal, which may enable reading of a laser marking and determination of identification information, may increase reliability of the gas-tight seal, and may preferably achieve lowering of an electronic component receiving package, and an electronic component receiving package using the same. A lid (1) for a gas-tight seal comprises: a first metal layer (2) having a flat panel shape; a second metal layer (3) provided on one side of the flat panel shape of the first metal layer (2); and an oxide layer (4) provided on the other side of the flat panel shape of the first metal layer (2). Chromium (Cr) of 2 to 8 wt% is detected from the cross section of the first metal layer (2) by SEM-EDX, Cr of equal to or less than 10 wt% is detected from the surface of the second metal layer (3) by SEM-EDX, and Cr of 10 wt% or greater is detected from the surface of the oxide layer (4) by SEM-EDX. An electronic component receiving package (10) is formed by coupling the lid (1) to a ceramic frame (14) receiving an electronic component (12) through a glass coupling layer (5).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a hermetic sealing lead,

The present invention relates to a hermetic sealing lead, a manufacturing method thereof, and an electronic component storage package using the same.

2. Description of the Related Art Conventionally, electronic components such as quartz crystal vibrators and the like are sealed in an airtight container in order to prevent deterioration of their characteristics. For example, the electronic component storage package 10 having the configuration shown in Fig. 1 has a structure in which the ceramic component 14, in which the lead 1 and the recessed electronic component housing portion 11a are formed, And an electronic part 12 such as a crystal oscillator supported by the bump 13 is hermetically sealed in the inside thereof. This hermetic sealing is caused by the lid 1 and the ceramic frame body 14 being bonded by the glass bonding layer 5 formed by melting and re-solidifying the glass material. In this case, if the lead 1 and the ceramic frame member 14 are made of the same ceramic material, since the thermal expansion coefficients of the leads 1 and the ceramic frame member 14 are the same, problems such as breakage due to expansion or contraction during hermetic sealing occur It is difficult to do. However, since the lead 1 using the ceramic material needs to have a large thickness in order to secure the mechanical strength that can withstand hermetic sealing, lowering of the electronic component housing package 10 is not easy.

[0005] A lead using a metal material capable of lowering the package of an electronic component by solving the above-described problem is disclosed in, for example, Patent Document 1. [ In the lead 1, the entire surface of the first metal layer as the substrate is covered with an oxide film layer containing Cr. The first metal layer is made of an Fe-42% Ni-6% Cr alloy (metal material) having a high mechanical strength that can withstand hermetic sealing and a coefficient of thermal expansion close to that of the ceramic frame body 14 . The oxide film layer covering the surface of the first metal layer is a black oxide film layer containing Cr formed by selectively oxidizing Cr contained in the first metal layer and has good wettability with the glass bonding layer 5. It is said that the lead 1 can lower the electronic component housing package 10 without impairing the hermetic sealability.

International Publication No. 2012/108083

In recent years, by irradiating a laser with a low output power for the purpose of identifying individual products (electronic component storage packages), the surface of the lead 1 shown in Fig. 1, which is not the glass bonding layer 5 side, (Hereinafter referred to as " laser marking "). However, laser marking is a laser irradiation mark by laser irradiation and is substantially black. Therefore, in the case of the lead 1 having the structure in which the whole surface disclosed in the above-mentioned Patent Document 1 is covered with the black oxide film layer containing Cr, the laser irradiation mark (laser marking) remaining on the surface of the black oxide film layer The reading is not easy and discrimination of the identification information of the laser marking can not be performed with high accuracy.

An object of the present invention is to provide a hermetic sealing lid capable of reading laser marking and discrimination of identification information and improving the reliability of the hermetic sealing and expecting low package weight and a method of manufacturing the hermetic sealing lid And an electronic component storage package using the hermetic sealing lead.

The inventor of the present invention has found that the aforementioned problems can be solved by newly providing a second metal layer which can suppress the blackening even at the formation temperature of the oxide film layer containing Cr and can maintain the original tone to some extent, .

That is, the hermetic sealing lead according to the present invention comprises a first metal layer in the form of a flat plate, a second metal layer provided on one surface of the flat plate of the first metal layer, and a second metal layer provided on the other surface of the flat plate shape of the first metal layer 10% by mass or less of Cr is detected by SEM-EDX on the cross section of the first metal layer, and 10% by mass or less of Cr is detected by SEM-EDX on the surface of the second metal layer , Cr exceeding 10 mass% is detected by SEM-EDX on the surface of the oxide film layer. The " SEM-EDX " according to the present invention also means an energy dispersive X-ray spectroscopy (EDX) attached to a scanning electron microscope (SEM).

In the hermetic sealing lead of the present invention, it is preferable that the surface provided with the oxide film layer has an annular groove.

Further, it is preferable to have a plurality of the annular grooves.

It is preferable that the sum of the thickness of the first metal layer and the thickness of the second metal layer is 20 to 100 mu m.

The hermetic sealing lid according to the present invention can be formed by the method of manufacturing the hermetic sealing lid of the present invention.

That is, the method for producing a hermetic sealing lead according to the present invention is a method for manufacturing a hermetic sealing lead according to the present invention, wherein SEM-EDX of a surface is formed on one surface of a first metal layer of a flat plate shape having 2 to 8 mass% A second metal layer having a Cr content of 1 mass% or less is bonded to the first metal layer and then the first metal layer is subjected to a heat treatment in a selective oxidizing atmosphere having a holding temperature of 800 ° C. to 1150 ° C., An oxide film layer having Cr exceeding 10 mass% is formed.

In the method of manufacturing a hermetic sealing lead of the present invention, a flat second metal material corresponding to the second metal layer is clad-bonded to one surface of a flat first metal material corresponding to the first metal layer And the second metal layer is bonded to one surface of the first metal layer.

Alternatively, metal plating corresponding to the second metal layer may be performed by exposing one side of the flat plate shape of the first metal layer and masking the other side, And the second metal layer may be bonded.

The selective oxidizing atmosphere is preferably a wet hydrogen atmosphere controlled at (dew point + 10) ° C to (dew point +40) ° C.

It is also preferable to form an annular groove by removing a part of the surface of the oxide film layer.

It is possible to obtain an electronic component storage package in which any one of the airtight sealing leads according to the present invention and the ceramic frame body housing the electronic components are coupled through the glass bonding layer.

In the electronic component storage package of the present invention, it is preferable that the thermal expansion coefficient? 1 (/ C) of the glass bonding layer and the thermal expansion coefficient? 2 (/ C) of the first metal layer are in the range of 30 to 250 占 폚, -7 ?? 2 -? 1 ? 5 × 10 -7 .

It is preferable that the thermal expansion coefficient alpha 1 (/ C) of the glass bonding layer and the thermal expansion coefficient alpha 3 (/ C) of the ceramic frame body satisfy a relationship of 0 ?? 1- It is preferable to satisfy the relationship.

It is preferable that the glass bonding layer is formed using a glass material having Pb of 1000 ppm or less. The glass material is preferably a glass material generally known as a low-melting glass material.

According to the hermetic sealing lead of the present invention, it is possible to easily and highly accurately identify and read the marking made of the black laser irradiation mark station, and improve the hermetic sealing property of the electronic component housing package.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing a schematic configuration of an electronic component storage package using a hermetic sealing lead; Fig.
2 is a cross-sectional view of one embodiment of a hermetic sealing lid of the present invention.
3 is a view showing a bottom surface (side where an oxide film layer is provided) of an embodiment of the hermetic sealing lead of the present invention.
FIG. 4 is a drawing showing a surface of a first metal layer heat-treated in a selective oxidation atmosphere (photograph). FIG.
Fig. 5 is a drawing (photograph) showing the surface of a second metal layer which is heat-treated in a selective oxidation atmosphere and bonded to one surface of the first metal layer shown in Fig. 4 according to the present invention.

An important feature of the present invention is that the blackening is suppressed even at the formation temperature of the oxide film layer containing Cr on one side of the hermetic sealing lead and the metal layer (second metal layer) capable of maintaining the original color tone to some extent . BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the hermetic sealing lead of the present invention will be described with reference to the drawings.

Fig. 2 shows a cross section of one embodiment of the hermetic sealing lead of the present invention. The lead 1 has a first metal layer 2 in the form of a flat plate, a second metal layer 3 bonded to one surface of the flat plate of the first metal layer 2, And an oxide film layer (4) containing Cr that covers the surface to which the two metal layers (3) are not bonded. The lead 1 is formed by bonding a second metal layer 3 to one surface of a first metal layer 2 and then performing a heat treatment in a selective oxidizing atmosphere having a holding temperature of 800 ° C or higher and 1150 ° C or lower, And a step of forming an oxide film layer 4 containing Cr on the surface of the metal layer 2 on which the second metal layer 3 is not bonded.

(First metal layer and an oxide coating layer)

In the present invention, Cr of 2 to 8 mass% is detected by the SEM-EDX of the cross-section, and the first metal layer 2 is formed into a flat plate shape suitable for the lead 1. By using a metal material in which 2 to 8 mass% of Cr is detected on the cross section of the first metal layer 2, the surface of the first metal layer 2 is subjected to heat treatment under specific conditions, It is possible to easily form the oxide film layer 4 containing Cr. In the oxide film layer 4 containing Cr, Cr exceeding 10 mass% is detected by SEM-EDX on the surface. By having such an oxide film layer 4, the molten glass material (hereinafter referred to as " molten glass ") before the glass bonding layer 5 shown in Fig. 1 is formed can be easily attached to the lead 1 . Even if molten glass is directly brought into contact with the surface of the first metal layer 2, the wet-diffusing property is deteriorated, and hermetic sealing is not easy. However, since the molten glass can be suitably wet-diffused on the surface of the oxide film layer 4 by contacting the molten glass to the surface of the oxide film layer 4 containing Cr, a suitable glass bonding layer 5 is formed The reliability of hermetic sealing is improved.

If the Cr detected in the cross section of the first metal layer 2 is less than 2 mass%, an oxide film layer 4 containing Cr exceeding 10 mass% is formed on the surface of the first metal layer 2 suitably . When the Cr detected in the cross section of the first metal layer 2 exceeds 8 mass%, the difference in thermal expansion from the glass bonding layer 5 or the ceramic frame 14 increases. As a result, problems such as breakage due to expansion or shrinkage during hermetic sealing are apt to occur. Therefore, it is supposed that 2 to 8 mass% of Cr is detected by the SEM-EDX of the cross-section of the first metal layer 2. In order to suitably form the oxide film layer 4 and reduce the above-described difference in thermal expansion, it is preferable that the Cr detected in the cross section of the first metal layer 2 is 3 to 7 mass%. Cr formed in the first metal layer 2 is likely to be selectively oxidized when the oxide film layer 4 is formed so that the Cr amount of the first metal layer 2 is liable to fluctuate. 2) as a whole is evaluated on the average, the Cr amount is maintained in the above-mentioned range.

Ni, Co, Ti, Si, Mn, Cu, Al, C, P, S, N, or the like other than Cr, as long as the first metal layer 2 does not impair the operation effect of the present invention. O, and the like. For example, SEM-EDX of the cross section shows that the first metal layer 2 is Fe-Cr based alloy in which Fe and 2-8 mass% Cr are detected, and 35-50 mass% Ni is detected Ni-Cr alloy such as Fe-42% Ni-6% Cr alloy, Fe-42% Ni-4% Cr alloy and Fe-47% Ni-6% Cr alloy. The Fe-Cr alloy in which 2 to 8 mass% of Cr is detected is subjected to heat treatment in a selective oxidizing atmosphere in a temperature range of 800 ° C. to 1150 ° C. to form an oxide film layer 4 containing Cr Can be easily formed. In addition, an Fe-Ni-Cr alloy in which 35 to 50 mass% of Ni is also detected is preferable because the coefficient of thermal expansion becomes small.

(Second metal layer)

In the present invention, the second metal layer 3 is bonded to one surface of the flat plate of the first metal layer 2, and Cr is detected as 10 mass% or less by SEM-EDX on the surface. The oxide film layer containing Cr is black as described above. Since the surface of the conventional lead 1 is black, even if the laser marking is performed as described above, it is not easy to read or interpret the identification information. Therefore, it is important that at least the surface area of the lead 1 on which laser marking is performed is not blackened. As shown in the figure, the above-mentioned Cr is added to one surface of the flat metal plate of the first metal layer 2 in an amount of 10% The second metal layer 3 is formed. Thereby, the second metal layer 3 can be made the second metal layer 3 having the blackening property. Such a Cr value is preferably as small as possible and the blackening of the surface of the second metal layer 3 is further suppressed. The surface showing this galvanizing property retains the original color tone before the heat treatment, for example, to such an extent that reading of the laser marking (laser irradiation mark) performed on the surface thereof and interpretation of the identification information are possible. In other words, if the Cr detected by the SEM-EDX on the surface of the second metal layer is 10 mass% or less, laser marking is performed on the surface, and the laser-marked characters and the like can be identified by an image processing apparatus or the like, (Second metal layer) has a negligible blackness.

However, when the heat treatment for forming the oxide film layer 4 with Cr exceeding 10 mass% detected by SEM-EDX on the surface, that is, the heat treatment by the selective oxidizing atmosphere having the holding temperature of 800 ° C or higher and 1150 ° C or lower is performed, The element (particularly Cr) contained in the first metal layer 2 diffuses into the second metal layer 3 and diffuses to the vicinity of the exposed surface of the second metal layer 3 or to the surface. An oxide may be formed on the exposed surface of the second metal layer 3 if an element (particularly Cr) which is easily oxidized is present near the exposed surface of the second metal layer 3 or on the surface thereof. Even in such a case, if the Cr detected by the SEM-EDX on the surface of the second metal layer 3 is 10 mass% or less, the exposed surface of the second metal layer 3 after the heat treatment shows a degree of blackening that can not withstand practical use There is no work. The oxidation phenomenon of the exposed surface of the second metal layer 3 due to such diffusion tends to proceed with an increase in the Cr content, and depending on the degree of oxidation, the laser marking (laser irradiation mark) And it becomes black to such an extent that interpretation of information identification is difficult. From this point of view, the Cr detected by the SEM-EDX on the surface of the second metal layer 3 after the formation of the oxide film layer 4 (the state after the heat treatment) is reduced, It was confirmed that when the amount is less than% by mass, it has a clear blackness.

In the present invention, the non-blackening property of the second metal layer 3 is not easily blackened in a selective oxidizing atmosphere in which the holding temperature is 800 占 폚 or more and 1150 占 폚 or less. Setting the holding temperature in the range of 800 DEG C or more and 1150 DEG C or less is a temperature at which it is easy to form an oxide film layer containing Cr on the surface of a metal material containing 2 to 8 mass% of Cr, This is because the holding temperature at the time of hermetic sealing is 1150 占 폚 or less. At a holding temperature exceeding 1150 占 폚, Cr contained in the first metal layer 2 is diffused in a large amount on the exposed surface of the second metal layer 3 or in the vicinity thereof, and the exposed surface of the second metal layer 3 There is a case in which blackening can not be tolerated for this practical use.

The material (metal) of the second metal layer 3 is preferably selected to be excellent in oxidation resistance and suitable for bonding with the first metal layer 2. Concretely, the Cr detected by the SEM-EDX on the surface of the second metal layer 3 after the formation of the oxide film layer 4 is 10 mass% or less and the Ni content is 65 mass% or more. The Ni content is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass. The material of the second metal layer 3 is ideally pure Ni and is preferably Ni-Cu alloy or Ni-P alloy. The other element is preferably Ti, Co, Pd, Ag, Au, Pt And the like. The second metal layer 3 may be formed by pure Ni plating, NiP plating, or the like.

The selective oxidation atmosphere referred to in the present invention refers to a selective oxidation atmosphere in which the first metal layer 2 in which Cr is detected by SEM-EDX at 2 to 8 mass% ), An oxidizing atmosphere in which Cr is preferentially selected and oxidized is intended. A preferred selective oxidizing atmosphere is a wet hydrogen atmosphere controlled at (dew point + 10) ° C to (dew point +40) ° C. Since such a wet hydrogen atmosphere has a low oxygen partial pressure, general metal elements other than Cr are hardly oxidized, and relatively easily oxidized Cr can be selectively oxidized. For example, in the case of the first metal layer 2 using the Fe-Ni-Cr alloy, among the main metal elements Fe, Ni and Cr included in the first metal layer 2, Oxidized. Therefore, the surface of the first metal layer 2, to which the second metal layer 3 is not bonded, can be easily covered with the oxide film layer 4 containing Cr.

(Bonding of the first metal layer and the second metal layer)

The configuration in which the second metal layer 3 is bonded to one surface of the first metal layer 2 in a flat plate shape is formed on one surface of the first metal material having a flat plate shape corresponding to the first metal layer 2, A cladding rolling method in which a second metal material having a flat plate shape corresponding to the first metal layer 2 is clad-bonded to the first metal layer 2 or a clad rolling method in which the first metal layer 2 is exposed on one side of a flat plate- 2 < / RTI > metal layer 3, and the like. For example, when pure Ni is used for the second metal layer 3, a structure in which the second metal layer 3 and the first metal layer 2 are suitably combined is obtained by either the clad rolling method or the one-side plating method . When a Ni-Cu alloy is used for the second metal layer 3, a Ni-Cu dissolving material whose alloy composition is easily adjusted is used for the second metal material, and a method of performing the clad rolling with the first metal material is suitable Do. When a Ni-P alloy having a low ductility is used for the second metal layer 3, the one-side plating method is more preferable than the clad rolling method involving plastic deformation.

(Glass bonding layer)

In the present invention, the glass bonding layer 5 is for hermetically sealing the electronic component housing package 10 by bonding the lead 1 and the ceramic frame member 14, as shown in Fig. Therefore, the glass bonding layer 5 is formed of a glass which is made of molten glass at the time of hermetic sealing and has an action and effect as an adhesive exhibiting good wettability with either the oxide film layer 4 of the lead 1 or the ceramic frame member 14 Materials are used. Since the glass material is generally fragile, it is preferable that the difference in thermal expansion to either of the first metal layer 2 of the lead 1 and the ceramic frame 14 is small.

For example, the thermal expansion coefficient α2 (/ ℃) the thermal expansion coefficient α1 (/ ℃) and the first metal layer (2) of the glass bonding layer (5), -15 × 10 -7 at a temperature range of 30~250 ℃ ? 2 -? 1? 5 10 - 7 . The coefficient of thermal expansion of the glass bonding layer 5 agrees with the coefficient of thermal expansion of the glass material used for the glass bonding layer 5. With this configuration, when the molten glass is cooled from the temperature at which the glass material is melted to the temperature at which the glass bonding layer 5 is formed in the bonding of the glass bonding layer 5 and the first metal layer 2, The stress generated in the glass bonding layer 5 due to the bonding with the lid 1 is reduced, so that cracking of the glass bonding layer 5 due to the stress can be prevented.

For example, when the thermal expansion coefficient? 1 (/ 占 폚) of the glass bonding layer 5 and the thermal expansion coefficient? 3 (/ 占 폚) of the ceramic frame body 14 satisfy 0?? 1- 10 x 10 < -7 > With this configuration, when the glass bonding layer 5 and the ceramic frame body 14 are bonded together and the molten glass solidifies from the temperature at which the glass material is melted to the temperature at which the glass bonding layer 5 is formed, The stress generated in the glass bonding layer 5 due to the bonding with the ceramic frame member 14 is reduced so that the glass bonding layer 5 or the ceramic frame member 14 caused by the stress can be prevented from being broken.

For example, when the glass material used for the glass bonding layer 5 is a V-based glass material of V 2 O 5 -P 2 O 5 -TeO-Fe 2 O 3 (thermal expansion coefficient α1 = with 10 -7 / ℃) to, and the first metal layer (2) of metal material for Fe-42% Ni-6% Cr alloy (thermal expansion coefficient α2 = 74 × 10 -7 / ℃ ) of 30~250 ℃ used for and, in the case where a ceramic frame body 14, the ceramic material Al 2 O 3 (thermal expansion coefficient α3 = 65 × 10 -7 / ℃ of 30~250 ℃) for use in, is 4 × 10 above α2-α1 - 7 / DEG C, and the aforementioned alpha 1 - alpha 3 is 5 x 10 < -7 > / DEG C, all of which are preferable in the present invention. The above-mentioned glass material is a glass material generally known as a low melting point glass material.

Next, a preferred embodiment of the hermetic sealing lead of the present invention will be described. 3 shows a bottom surface of an embodiment of the hermetic sealing lead of the present invention. The bottom surface referred to here is a surface opposite to the side where the second metal layer is provided as viewed from the lower side in the drawing, as shown in Fig. 2, and is a surface coupled with the ceramic frame body 14. [ In FIG. 3, the same reference numerals as used in FIG. 1 and FIG. 2 are used for the sake of simplicity.

(Annular groove)

The lead 1 shown in Fig. 3 is formed by setting an annular glass bonding region 6 to be bonded to the glass bonding layer 5 on the surface of the oxide film layer 4 and surrounding the glass bonding region 6 (2) having a first annular groove (7) and a second annular groove (8) on the inner side and the outer side (outer surface (6b) side) to be. The first annular groove 7 is formed by removing at least a part of the oxide film layer 4 so that the surface of the oxide film layer 4 can be separated discontinuously from the glass bonding region 6 and the inside 6a thereof Continuous grooves (including recesses and depressions) are intended. By forming the first annular groove 7, it is possible to prevent the molten glass from being wet-diffused into the inner side 6a which does not contribute to the bonding between the lid 1 and the ceramic frame 14 during hermetic sealing , And can be sufficiently wet-diffused into the glass-bonding region 6.

Like the first annular groove 7, the second annular groove 8 is formed by removing at least a part of the oxide film layer 4, and the surface of the oxide film layer 4 is covered with the glass bonding region 6 (Including concave or depressed portions) capable of discontinuously separating the outer side (the outer side 6b side) and the outer side (the outer side 6b side). By forming the second annular groove 8, it is possible to prevent the molten glass from wet-diffusing into the outer surface 6b which does not contribute to the bonding between the lid 1 and the ceramic frame 14 during hermetic sealing , And can be sufficiently wet-diffused into the glass-bonding region 6.

The effect of preventing the wetting and diffusion of the molten glass to the inside 6a by the above-described first annular groove 7 causes the inside of the electronic component housing package 10 to be contaminated by the glass material, Malfunction of the electronic component 12 can be prevented. In addition, due to the effect of preventing the wetting and diffusion of the molten glass to the outer surface 6b by the above-described second annular groove 8, the outer surface of the electronic component housing package 10 is contaminated by the glass material, Can be prevented. The first annular groove 7 and the second annular groove 8 as shown in Fig. 3 are formed by a method of trimming (trimming) at least a part of the oxide film layer 4 by laser irradiation with a high output It can be easily formed.

(Thickness of lead)

In the present invention, the sum of the thickness of the first metal layer 2 and the thickness of the second metal layer 3 (hereinafter referred to as " thickness of the metal layer ") is preferably 20 to 100 m. The thickness of such a metal layer is a suitable range for contributing to a practical level of lowering required for the electronic component housing package 10. When the thickness of the metal layer exceeds 100 탆, the electronic component housing package 10 tends to be large-sized, and therefore, it may not contribute to a low level of practical use. When the thickness of the metal layer is less than 20 mu m, the low package effect of the electronic component housing package 10 appears, but the rigidity is remarkably lowered, so that the mechanical strength required for the hermetic sealing lead may not be obtained. In consideration of the relationship between the lowering and the mechanical strength, the thickness of the metal layer is more preferably 30 to 90 占 퐉.

The hermetic sealing lead of the present invention has an oxide film layer 4 as shown in Fig. When the above-described holding temperature is 800 to 1150 占 폚, the thickness of the oxide film layer 4 is about 0.1 to 2 占 퐉. Therefore, the value obtained by dividing the ratio of the thickness of the oxide film layer 4 to the total thickness of the lead 1, that is, the thickness of the oxide film layer / (the thickness of the metal layer + the thickness of the oxide film layer) R TO ) is about 9% (2 탆 / (20 탆 + 2 탆) x 100%) even when the thickness of the metal layer is 20 탆 and the thickness of the oxide film layer 4 is 2 탆. As a result, there is no likelihood that the lowering of the electronic component housing package 10 is impeded by the presence of the oxide film layer 4.

The hermetic sealing lead of the present invention is preferably made of the same material as the first metal layer 2 and the second metal layer 3 so as to suppress the warpage of the lead 1 caused by the difference in thermal expansion between the first metal layer 2 and the second metal layer 3, (R T2 ) obtained by the ratio of the thickness of the first metal layer 3, that is, the thickness of the second metal layer / the thickness of the metal layer x 100% is preferably as small as possible and preferably 2 to 35%. For example, when the thickness of the metal layer is 100 탆 and the thickness of the second metal layer 3 is 2 탆, the R T2 value is 2%, the thickness of the metal layer is 20 탆, and the thickness of the second metal layer 3 is 7 Mu m, the R T2 value is 35%.

(Electronic component storage package)

The electronic part storage package 10 (Fig. 1) having a configuration in which the lead 1 shown in Fig. 1 is replaced with the lead 1 shown in Fig. 2 by using any one of the hermetic sealing leads of the present invention described above ) Can be obtained. Concretely, the lead frame 1 (the lead 1 shown in Fig. 2) and the ceramic frame body 14 in which the electronic component 12 is housed are joined together via the glass bonding layer 5, And is a storage package 10. On the opposite surface of the lead 1 not on the side of the glass bonding layer 5, a second metal layer 3 having a blackening property is provided. Therefore, by performing laser marking on the surface of the second metal layer 3 having a blackening property, reading and discrimination of laser marking as a black laser irradiation mark can be easily and accurately performed.

In the embodiment of the electronic component housing package 10, for example, glass materials such as Pb-based, Bi-based, and V-based glass can be used for the glass bonding layer 5. From the viewpoint of environmental protection, it is preferable that such a glass material has a Pb content of 1000 ppm or less as a harmful substance. The Pb content of 1000 ppm or less is based on the RoHS directive. Further, from the viewpoint of lowering the sealing temperature at the time of hermetic sealing, it is more preferable to use a low melting point glass material of the V system. For example, a glass material having a composition of V 2 O 5 -P 2 O 5 -TeO 2 -Fe 2 O 3 having a low melting point of, for example, about 320 to 400 ° C is P 2 O 5 or P By changing the content of 2 O 5 -TeO 2 , hermetic sealing in a temperature range of about 350 to 420 ° C. is possible. As the hermetic sealing method, for example, a glass paste prepared by blending a glass material with a binder or the like is applied to the glass bonding region 6 set on the surface of the oxide film layer 4 of the lead 1, A method of reflowing the glass paste by placing the lead 1 in contact with the ceramic frame member 14 at an appropriate position and setting the holding temperature at about 370 to 420 DEG C can be applied.

[Example]

Hereinafter, the present invention will be described and explained in detail. However, the embodiments according to the present invention are not limited to the embodiments described herein.

The lead-in-lead (1) of the present invention comprises Ni of more than 90 mass% in material, and substantially does not contain Cr in relation to the first metal layer (2) of which the material is Fe-42Ni-6Cr alloy The second metal layer 3 is clad-bonded, and is unified by press working. The thickness of the first metal layer 2 of the discrete lead 1 is 77 占 퐉, and the thickness of the second metal layer 3 is 3 占 퐉. The discretized lead 1 was subjected to a heat treatment for 30 minutes in a furnace at a holding temperature of 850 DEG C and a wet hydrogen atmosphere at a dew point of 23.5 DEG C to form an oxide film layer 4 containing Cr, To prepare a lead (1).

Fig. 4 shows the surface appearance of the first metal layer 2 and Fig. 5 shows the surface appearance of the second metal layer 3 with respect to the lead 1 thus produced. As shown in Fig. 4, the surface of the first metal layer 2 is blackened by the above-mentioned heat treatment. On the other hand, as shown in Fig. 5, the surface of the second metal layer 3 is blackened, The original color tone of the former was maintained to some extent. When the surface of the second metal layer 3 was subjected to laser irradiation, it was possible to read the laser marking (laser irradiation mark) and to analyze the information identification.

Next, the cross section of the first metal layer 2 before and after the heat treatment, the surface of the second metal layer 3 before and after the heat treatment, and the surface of the oxide coat layer 4 formed after the heat treatment were measured by SEM-EDX Each analysis was performed. EDX (type Emax xact) of Horiba Seisakusho Co., Ltd., attached to SEM (type S-3400N) manufactured by Hitachi High-Technologies Corporation was used for SEM-EDX. The various conditions of the SEM and EDX were an acceleration voltage of 15 kV, a working distance of 10 mm, a measurement time of 50 sec, and a collection count rate of 2 to 3 kpcs. In SEM-EDX, an area of 10 mu m in one side of the inspected object was measured at three places, and an arithmetic mean value was obtained and used as a detection value. The sample of the first metal layer 2 is measured with a center of a portion shifted by about 15 占 퐉 toward the inside of the first metal layer 2 from the approximate boundary with the oxide film layer 4 after the end face of the sample is polished Respectively. The surface of the second metal layer 3 and the surface of the oxide film layer 4 were measured approximately in the vicinity of the center.

Table 1 shows the measurement results by SEM-EDX. The content ratios of other elements other than Cr, Fe, Ni and O are changed before and after the heat treatment in each case, but this is considered to include the influence of surface contamination caused by contaminants in the heat treatment furnace or in the atmosphere. Further, in the first metal layer after the heat treatment, the content ratio of the ternary element is small, but it is considered that this is because the measurement of the polished surface after polishing is less likely to be affected by the surface contamination described above. Also, "-" shown in Table 1 is intended to be below the measurement limit.

Figure pat00001

As shown in Table 1, the surface of the second metal layer 3 of the lead 1 after the heat treatment was found to contain Cr of 4.44 mass%, which is 10 mass% or less, and 65 mass% or more, 70% by mass or more of Ni was detected. The surface of the second metal layer 3 was subjected to laser irradiation to read the laser marking (laser irradiation mark) and to analyze the information, so that information could be normally detected.

On the surface of the first metal layer 2 after the heat treatment, a blackened oxide film layer 4 as a whole was formed, and Cr of 20.24 mass% was detected in an amount exceeding 10 mass%. The surface of the oxide film layer 4 was subjected to laser irradiation to attempt to read the laser marking (laser irradiation mark) or to analyze the information, but it was difficult to discriminate the information. Furthermore, even in the case of the oxide film layer 4 having a Cr content exceeding 10 mass%, the wettability with the molten glass using the hermetically sealing glass material was good.

The lead 1 manufactured as described above and the electronic component housing member 11 are made of a glass material having a composition of V 2 O 5 -P 2 O 5 -TeO 2 -Fe 2 O 3 (softening point: about 320 to 360 ° C) , And the glass paste was reflowed by setting the holding temperature at about 400 占 폚. As a result, it was confirmed that the lead 1 and the electronic component housing member 11 were bonded to each other through the glass bonding layer 5, and the hermetic sealability was good.

1: Lead
2: first metal layer
3: Second metal layer
4: Anodizing layer
5: glass bonding layer
6: glass bonding area
6a: medial side
6b: outer surface
7: a first annular groove
8: a second annular groove
10: Electronic component storage package
11: Electronic component housing member
11a: Electronic component housing part
12: Electronic parts
13: Bump
14: Ceramic frame body

Claims (13)

A first metal layer having a flat plate shape; a second metal layer provided on one surface of the flat plate shape of the first metal layer; and an oxide film layer provided on the other surface of the flat plate shape of the first metal layer,
2 to 8 mass% of Cr is detected by SEM-EDX in the cross section of the first metal layer, Cr of 10 mass% or less is detected by SEM-EDX on the surface of the second metal layer, Wherein a Cr exceeding 10 mass% is detected by SEM-EDX. The method according to claim 1,
And an annular groove is formed in a surface of the oxide film layer on which the oxide film layer is formed. 3. The method of claim 2,
And a plurality of said annular grooves. The method according to claim 1,
Wherein the total of the thickness of the first metal layer and the thickness of the second metal layer is 20 to 100 占 퐉. A second metal layer having a Cr content of not more than 1% by mass detected by SEM-EDX on the surface is bonded to one surface of a first metal layer in a flat plate shape having a Cr content of 2 to 8% by mass detected by SEM-EDX of the cross section, Wherein the heat treatment is performed in a selective oxidizing atmosphere having a holding temperature of 800 ° C or higher and 1150 ° C or lower, and an oxide film layer having Cr exceeding 10% by mass detected by SEM-EDX on the surface of the other surface of the first metal layer And the Cr formed on the surface of the second metal layer by SEM-EDX is 10 mass% or less. 6. The method of claim 5,
And a second metal material having a flat plate shape corresponding to the second metal layer is clad-bonded to one surface of the first metal material having a flat plate shape corresponding to the first metal layer, Wherein the sealing member is formed by bonding the sealing member to the sealing member. 6. The method of claim 5,
The metal layer corresponding to the second metal layer is subjected to metal plating in a state in which one surface of the first metal layer is exposed and one surface of the second metal layer is masked, Wherein a metal layer is bonded to the metal layer. 6. The method of claim 5,
Wherein the heat treatment is performed in a wet hydrogen atmosphere controlled at (dew point + 10) ° C to (dew point + 40) ° C. 6. The method of claim 5,
Wherein an annular groove is formed by removing a part of a surface of the oxide film layer. An electronic component storage package, wherein the hermetic sealing lead according to any one of claims 1 to 4 and a ceramic frame body containing electronic components are coupled through a glass bonding layer. 11. The method of claim 10,
The thermal expansion coefficient α1 (/ ℃) and the thermal expansion coefficient α2 (/ ℃) of the first metal layer of the glass layer is bonded in a temperature range of 30~250 ℃ -15 × 10 -7 ≤α2- α1≤5 × 10 - 7 < / RTI > 11. The method of claim 10,
(/ ° C) of the glass bonding layer and the thermal expansion coefficient? 3 (/ ° C) of the ceramic frame satisfy a relationship of 0 ?? 1 -? 3? 10 占 10 - 7 in a temperature range of 30 to 250 占 폚 Electronic component storage package. 11. The method of claim 10,
Wherein the glass bonding layer is a glass material having Pb of 1000 ppm or less.
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