TW201238857A - Cover material for airtight sealing, package for housing electronic components, and method for manufacturing cover material for airtight sealing - Google Patents

Cover material for airtight sealing, package for housing electronic components, and method for manufacturing cover material for airtight sealing Download PDF

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TW201238857A
TW201238857A TW100142851A TW100142851A TW201238857A TW 201238857 A TW201238857 A TW 201238857A TW 100142851 A TW100142851 A TW 100142851A TW 100142851 A TW100142851 A TW 100142851A TW 201238857 A TW201238857 A TW 201238857A
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layer
metal substrate
thermal expansion
expansion coefficient
electronic component
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TW100142851A
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Chinese (zh)
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TWI516423B (en
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Masaharu Yamamoto
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Neomax Materials Co Ltd
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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
    • H01L23/02—Containers; Seals
    • H01L23/04—Containers; Seals characterised by the shape of the container or parts, e.g. caps, walls
    • H01L23/053—Containers; Seals characterised by the shape of the container or parts, e.g. caps, walls the container being a hollow construction and having an insulating or insulated base as a mounting for the semiconductor body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/10—Containers; Seals characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container
    • 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
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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]
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/05—Holders; Supports
    • H03H9/10—Mounting in enclosures
    • H03H9/1007—Mounting in enclosures for bulk acoustic wave [BAW] devices
    • H03H9/1014—Mounting in enclosures for bulk acoustic wave [BAW] devices the enclosure being defined by a frame built on a substrate and a cap, the frame having no mechanical contact with the BAW device

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)

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

201238857 六、發明說明： 【發明所屬之技術領场^ 本發明係關於氣密密刼田掌 在封用盍材、電子零件收納用盒及氣密 密封用蓋材之製造方法。 【先前技術】 過去’已知冑種電子零件收納用盒，其係使用由含有201238857 VI. Description of the Invention: [Technical Fields of the Invention] The present invention relates to a method for manufacturing a sealed coffin, an electronic component storage case, and a hermetic sealing cover material. [Prior Art] In the past, a known electronic component storage case was used.

Pb之焊錫或玻璃所構成的接合層’將蓋材與由陶兗材料所 構成之電子零件_構材’依收納有電子零件的狀態進行氣 密密封。然而’由於在電子零件收納用盒中使用含有Pb之 焊踢或玻璃’❿Pb為有害物質故不佳，而要求不含有Pb 的接合材料。 另外’於蓋材使用陶变材料時，有因蓋材厚度變大而電子 零件收納用盒大型化的不良情形。因此，要求使用能較陶£ 材料更加減小蓋材厚度之金屬材料作為蓋材。 因此，提案有-種電子零件收納用盒，其係使用由不4 Pb之Au-20Sn合金所構成的接合層，將由金屬材料所制 之蓋材、與由㈣材料所構成之電子零件收納構材進行氣键 密封。該Au-20Sn合金因融點低（約28(rc)，故可抑制戶 納之電子零件因熱而發生劣化的情形。然而，Μ高價Μ 要求Au-20Sn合金的替代材料。 抵 考慮上述事項，習知提案有一種電子零件收納用盒 使用非AU-20Sn合金而*由玻璃材料所構成的接合屬了系 9 將 100142851 201238857 由金屬材料所構成之蓋材、與由陶£材_構成之電子愛件 收納構材進行氣密密封。此種電子零件收納用盒已揭示於例 如曰本專利特開2002-26679號公報。 上述日本專利特開2002_26679號公報中，揭示有一種表 面安裝型之水晶振逢器（電子零件收納用盒），其具備·水晶 振盪器；含有用於收納水晶振盪器之凹部與形成於凹部周= 的框部之陶究盒；與金屬蓋。此表面安裝型之水晶振盈器的 金屬蓋，係由鍍Ni之Fe系合金(科伐合金）、或含有42質 量％之Ni與6質量％之Cr與Fe的Fe系合金(426合金)所構 成。又，表面安裝型之水晶振盪器中，由於藉低融點玻璃使 陶瓷盒之框部與金屬蓋接合，故使水晶振盪器氣密密封於陶 瓷盒内。 然而’上述日本專利特開2002-26679號公報所揭示之表 面女裝型之水晶振篕益中’認為由於金屬蓋係由鑛Ni之 系合金(科伐合金）、或426合金所構成，故有金屬蓋之表面 金屬層與低融點玻璃未充分密黏之虞。此時，有無法充分確 保表面安裝型之水晶振盪器（陶瓷盒)之氣密性的問題點。 【發明内容】 本發明係為了解決上述課題而形成者，本發明之一目的在 於提供使用不含Pb之玻璃材料，而可充分確保電子零件收 納用盒之氣密性的氣密密封用蓋材、電子零件收納用盒及氣 密密封用蓋材之製造方法。 100142851 201238857 " 發明之氣密密封用蓋材，係由陶瓷材料所構 成’使用於含有用於 收肩電子零件之電子零件收納構材的電 子零件收納用念 ’-具備：金屬基材，其包含至少含右The bonding layer constituting the solder or glass of Pb is hermetically sealed in a state in which the electronic component is formed by the lid member and the electronic component constituting the ceramic material. However, it is not preferable to use a welding kick containing Pb or a glass ❿Pb as a harmful substance in the electronic component storage case, and a bonding material containing no Pb is required. In addition, when the ceramic material is used for the cover material, there is a problem that the thickness of the cover material is increased and the size of the electronic component storage case is increased. Therefore, it is required to use a metal material which can reduce the thickness of the cover material more than the ceramic material as the cover material. Therefore, there is proposed an electronic component storage case which uses a bonding layer made of an Au-20Sn alloy which is not 4 Pb, and a cover member made of a metal material and an electronic component storage structure made of the (4) material. The material is sealed by a gas key. The Au-20Sn alloy has a low melting point (about 28 (rc), so it can suppress the deterioration of the electronic parts of the households due to heat. However, the high price Μ requires an alternative material for the Au-20Sn alloy. It is a conventional proposal to use a non-AU-20Sn alloy for an electronic component storage case and a joint of a glass material. The cover member made of a metal material is composed of 100142851 201238857 and is composed of a ceramic material. The electronic accessory housing member is hermetically sealed. Such an electronic component storage case is disclosed in, for example, Japanese Patent Laid-Open Publication No. 2002-26679. Crystal vibrating device (electronic component storage box), which includes a crystal oscillator, a ceramic box containing a concave portion for accommodating a crystal oscillator and a frame portion formed in the recessed portion = and a metal cover. The metal cover of the crystal vibrator is made of a Ni-plated Fe-based alloy (Kovar) or a Fe-based alloy (426 alloy) containing 42% by mass of Ni and 6% by mass of Cr and Fe. , surface mount type In the crystal oscillator, since the frame portion of the ceramic case is joined to the metal cover by the low-melting glass, the crystal oscillator is hermetically sealed in the ceramic case. However, the above-mentioned Japanese Patent Laid-Open Publication No. 2002-26679 discloses The surface of the women's type of crystal vibrating is considered to be because the metal cover is composed of Ni alloy (Kovar) or 426 alloy, so the surface metal layer of the metal cover is not sufficiently dense with the low melting point glass. In this case, there is a problem that the airtightness of the surface mount type crystal oscillator (ceramic case) cannot be sufficiently ensured. [Invention] The present invention has been made to solve the above problems, and an object of the present invention is A method for producing a hermetic sealing cover material, an electronic component storage case, and a hermetic sealing cover material which can sufficiently ensure the airtightness of the electronic component storage case by using a glass material containing no Pb. 100142851 201238857 &quot The invention relates to a cover material for hermetic sealing, which is composed of a ceramic material and is used for the storage of electronic components containing electronic component storage members for shoulder electronic components. Metal substrate, comprising at least a right-containing

Cr之金屬材料；拙 ^ 铍覆層，係形成於金屬基材之表面上，由Cr metal material; 拙 ^ 铍 coating, formed on the surface of the metal substrate,

Cr之軋化皮膜所捲. 上，由不含Pbh 、接合層，係形成於被覆層之表面 之成有被覆層 且第1發明之氣密密封用蓋材中，係如上述般，藉由 :皮”：金屬基材之表面上且由。之氧化皮膜所構成的 $復曰、、、形成於被覆層表面上且由不含pb之玻璃材料所 冓成並用於將形成有被覆層的金屬基材與電子零件收納構 材接合的接合層，而可使構成被㈣之〇氧化皮膜、與構 成接。層之麵材料充分密黏，故可將金屬基材與電子零件 收輯材充分接合。因此，可使用不含Pb之玻璃材料，而 充刀確保電子零件收納用盒之氣密性。又，藉由具備包含至 少 Cr 之 ® I屬材料的金屬基材，則相較於在基材中使用了 陶竟材料的^兄’可更加減小氣密密封用蓋材的厚度，故可 抑制電子零件收_盒之大型化。又，藉蚊金屬基材包含 至少含Cr夕乂v ^ 金屬材料，則可容易於金屬基材表面上形成由 °*之氧化皮膜所構成的被覆層。 卜第1 反In the case of the rolled film of Cr, the cover sheet which is formed on the surface of the coating layer and which is formed on the surface of the coating layer without the Pbh and the bonding layer, and the hermetic sealing cover material of the first invention is as described above. : "skin": a ruthenium formed on the surface of a metal substrate and composed of an oxide film, formed on the surface of the coating layer and formed of a glass material not containing pb and used for forming a coating layer. The bonding layer in which the metal substrate and the electronic component housing member are joined together can sufficiently form the surface of the layered material of the layer formed by the (4) tantalum oxide film, so that the metal substrate and the electronic component collection material can be sufficiently Therefore, it is possible to use a glass material which does not contain Pb, and the filling knife ensures the airtightness of the electronic component storage case. Further, by providing a metal substrate containing at least Cr of the genus I, it is compared with The use of the ceramic material in the base material can reduce the thickness of the cover material for hermetic sealing, so that the size of the electronic component can be suppressed. Further, the metal substrate of the mosquito contains at least Cr. ^ Metal material can be easily formed on the surface of metal substrate Coating layer is formed of an oxide film ° * constituted. The first counter-Bu

' I明之氣密密封用蓋材中，較佳係構成為於30°C 以上且 250V ^ ^ m 下之溫度範圍，接合層之熱膨脹係數ai(/〇C) 100142851 201238857 與金屬基材之熱膨脹係數α2(Γ〇滿足· α1^5χ10_7的關係。若如此構成，則在由使 二〜 層接合時之溫度起降低溫度時，可使由朗材料㈣成2 合層中所發生的應力減小，故可抑制由玻璃材料所 合層中發生破裂（裂痕）的情形。 接 上述第1發明之氣密密封用蓋材中，較佳係被覆層之厚度 為〇>以上。若為此種構成，則可充分確保被覆層厚/ 故可使構成減層之氧化㈣、與構成接合層之^璃 材料確貫密黏。 上述第i發明之氣密密封用蓋材中，較佳係金屬基材含有 Ni、3質量。/。以上且6質量％以下之&與以的以系合金。 若為此種構成，則因金屬基材係由含有3質量％以上之〇 的Fe系合金所構成’故可於金屬基材表面上確實形成由^ 氧化皮膜所構成的被覆層。又，藉由使金屬基材為由含有6 質量％以下之Cr的Fe系合金所構成，貝㈣&之過剩含量 所造成的金屬基材之_脹餘變大，而可抑制金屬基材之 熱膨脹係數與接合層之熱膨脹係數顯著相異的情形。因此 可抑制由於熱膨脹差異而造成之破裂等發生於接合層或金 屬基材中的情形。又’藉由使金屬基材含有Ni則可減小金 屬基材之熱恥脹係數，故可使金屬基材之熱膨脹係數較一般 金屬材料更加接近由熱膨脹係數較小之玻璃材料所構成之 接合層的熱膨服係數。 100142851 6 201238857 此時，較佳係金屬基材為由42質量％之Ni、3質量％以 且6貝里/〇以下之Cr與&的以系合金所構成。若為此 構成，則因金屬基材含有42 f量％之Ni而可確實減小 基材之熱膨脹係數，故可使金屬基材之熱膨脹係數確 由熱膨脹龜較小之玻璃材料所構叙接合層的熱膨 數。又，藉由使金屬基材為由含有42質量％之见與旦 %以上且6質里％以下之&的卜系合金所構成，故可構 為，接合層之熱膨脹魏α1與金屬基材之熱祕係數 確貫滿足训〇，、α2 —化5導7的關，而可確實抑 由玻璃材料所構成之接合層中發生破裂的情形。又，本 明者已針對此點藉實驗完成確認。 ” 上述第|明之氣密密封用蓋材中，較佳係使被覆層 於接。層所配置之金屬紐之表面上、及與接合層所配置 為相反側的金屬基材之表面上。若為此種構成，則與僅在全 屬基材之兩表面上之其中-面上形成被覆層的情形不同，^ 防止將接合層錯誤形成於未形成有被制之金屬基 上的情形。 材表面 上述第1發明之氣密密封用蓋材中，較佳係金屬 至少含有配置於接合層側並至少含有Cr之第】層才為由 與第1層不同之金屬材料之第2相包層材所構I老2 種構成，助較於金聽材為勤】層 為此 100142851In the lid member for hermetic sealing, it is preferably configured to have a temperature expansion range of 30 ° C or more and 250 V ^ ^ m, and a coefficient of thermal expansion of the bonding layer ai (/〇C) 100142851 201238857 thermal expansion of the metal substrate The coefficient α2 (Γ〇 satisfies the relationship of α1^5χ10_7. If it is configured as such, when the temperature is lowered by the temperature at which the two layers are joined, the stress generated in the two-layered layer of the material (4) can be reduced. Therefore, it is possible to suppress the occurrence of cracks (cracks) in the layer formed by the glass material. In the lid member for hermetic sealing according to the first aspect of the invention, the thickness of the coating layer is preferably 〇 > or more. In addition, it is possible to sufficiently ensure the thickness of the coating layer, so that the oxidation (4) constituting the reduction layer can be surely adhered to the glass material constituting the bonding layer. In the lid member for hermetic sealing of the above-mentioned i-th invention, a metal base is preferred. In the case of the above-mentioned structure, the metal substrate is made of a Fe-based alloy containing 3% by mass or more of ruthenium. The composition "is indeed formed on the surface of the metal substrate by the oxide film In addition, the metal substrate is made of a Fe-based alloy containing 6% by mass or less of Cr, and the excessive content of the shell (4) & The case where the thermal expansion coefficient of the metal substrate is remarkably different from the thermal expansion coefficient of the bonding layer is suppressed. Therefore, the occurrence of cracking or the like due to the difference in thermal expansion occurring in the bonding layer or the metal substrate can be suppressed. The inclusion of Ni reduces the thermal expansion coefficient of the metal substrate, so that the thermal expansion coefficient of the metal substrate can be closer to the thermal expansion coefficient of the bonding layer composed of the glass material having a smaller thermal expansion coefficient than the general metal material. 6 201238857 In this case, the metal base material is preferably a base alloy of 42% by mass of Ni, 3% by mass, and 6 or less of copper and / or less. The substrate contains 42% by volume of Ni and can reliably reduce the thermal expansion coefficient of the substrate, so that the thermal expansion coefficient of the metal substrate can be made by the glass material having a smaller thermal expansion turtle to clarify the thermal expansion of the bonding layer. borrow The metal substrate is made of a silicon alloy containing 42% by mass and more than 8% by weight and less than 6% by mass, so that the thermal expansion of the bonding layer, Wei α1, and the heat of the metal substrate can be configured. The coefficient satisfies the training, and the α2 - 5 guide 7 is closed, but it can be confirmed that the crack occurs in the joint layer composed of the glass material. Moreover, the present inventors have confirmed the experiment by this point." In the above-mentioned first sealing member for hermetic sealing, it is preferable that the coating layer is formed on the surface of the metal core disposed on the layer and on the surface of the metal substrate disposed on the opposite side of the bonding layer. Such a configuration is different from the case where the coating layer is formed only on the inner surface of both surfaces of the entire substrate, and the bonding layer is prevented from being erroneously formed on the metal substrate on which the metal substrate is not formed. In the surface-sealing lid member according to the first aspect of the invention, it is preferable that the metal layer contains at least a layer disposed on the side of the bonding layer and containing at least Cr, and the second phase of the metal material different from the first layer. The structure of the layer I consists of two old ones, which is better than the gold material.

將熱膨脹係數相異之異種之金屬材料彼此接合，可容易ZIt is easy to bond metal materials of different kinds of thermal expansion coefficients to each other.

SS

ΙΛΛΐ/fOOCI 201238857 金屬基材的熱膨脹係數。又，藉由於接合層側配置至少含有 Cr的第1層，則可在對應於接合層所形成之區域的金屬基 材表面上，容易形成由Cr氧化皮膜所構成的被覆層。 此時，較佳係第1層之熱膨脹係數大於接合層之熱膨脹係 數，第2層之熱膨脹係數小於接合層之熱膨脹係數。若為此 種構成，則藉由調整第1層之厚度與第2層之厚度，可使金 屬基材整體之熱膨脹係數接近接合層之熱膨脹係數。 上述金屬基材為由至少含有第1層與第2層之包層材所構 成的氣雄、後、封用蓋材中，較佳係金屬基材之第1層為由含有ΙΛΛΐ/fOOCI 201238857 Thermal expansion coefficient of metal substrates. Further, since the first layer containing at least Cr is disposed on the side of the bonding layer, the coating layer composed of the 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 preferred that the thermal expansion coefficient of the first layer is larger 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. According to this configuration, by adjusting the thickness of the first layer and the thickness of the second layer, the thermal expansion coefficient of the entire metal substrate can be made close to the thermal expansion coefficient of the bonding layer. The metal substrate is a gas-bearing, post-sealing or sealing cover material comprising at least a cladding material of the first layer and the second layer, and preferably the first layer of the metal substrate is contained.

Ni、3質量％以上且6質量％以下之〇與Fe的Fe系合金所 構成。若為此種構成’則可在對應於接合層所形成之區域的 金屬基材表面上，確實形成由Cr氧化皮膜所構成的被覆 層又藉由使金屬基材之第1層為由含有见之Fe系合金 所構成，則可減小第丨層之熱膨脹係數，故可使金屬基材之 熱膨脹係數接近由熱膨脹雜較奴麵材料所構成之接 合層的熱膨脹係數。 上述金屬基材為由至少含有第i層與苐2層之包層材所構 成的氣密㈣用歸巾，較佳係金屬基材為由含有下述層之 包層材所構成：配置於接合層側，至少含有&的第i層； 配置於第1層之與接合層為相反側，含有與第i層不同之金 屬材料的第2層；與配置於第2層之與第i層為相反側，至 少含有Cr之第3層。若為此種構成，則可使位於金屬基材 100142851 201238857 表面側之第1層與第3層分顺成為至少含有Q， 金屬基材之兩表面（第1層之與第2層為相反側的面及第於 層之與第2層為相反側的面)上分卿成由α之氧化皮^ 3 構成的被覆層。藉此，與僅在金屬基材之兩表面上之、所 面形成有被覆層的情況相異、中一 成有被覆層之金屬基材表面上/止接3層錯_成於未形 上述金屬基材為由含有第1層與第2層與第3層 所構成的氣密料職財，較佳㈣ ^^材 含有Ni、3暂旦〇/ 弟層均為由 合金所構成。:二=質量%以下之…與、系 層均一==金屬基材之第1層及第3 層之熱_'數二 =’故可減小第1層及第3 θ 可使至屬基材整體之熱膨脹m ρ =熱_係數較小之玻璃材料所構成之接合 蓋成 禾i層及苐3層均由含有42質量 質量％之心、鱼^的只么人人 貝里4之沁、6 系合金所構成，第2層為由含有 “、。之、與Fe的卜系合金所構成。根據 糟由使金屬基材m2層及第3層均由構成曾 量％之犯的μ合金所構成，則可確 質 層及第—服係數。因此，可使金屬基：層二 數確實接近由熱膨脹係數較小之玻璃材料所構成 100142851 θ 201238857 的熱膨脹係數。又，第1層及第3層均由含有42質量。/之Ni, 3% by mass or more and 6% by mass or less of bismuth and Fe Fe-based alloy. According to this configuration, it is possible 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 first layer of the metal substrate contain When the Fe-based alloy is formed, the thermal expansion coefficient of the second layer can be reduced, so that the thermal expansion coefficient of the metal substrate can be made close to the thermal expansion coefficient of the bonding layer composed of the thermal expansion material. The metal substrate is an airtight (four) filler made of a cladding material containing at least an i-th layer and a second layer. Preferably, the metal substrate is composed of a cladding material having the following layer: On the bonding layer side, at least the i-th layer of & is disposed on the opposite side of the first layer from the bonding layer, and includes a second layer different from the i-th layer; and is disposed on the second layer and the i-th layer The layer is on the opposite side and contains at least the third layer of Cr. According to this configuration, the first layer and the third layer on the surface side of the metal base material 100142851 201238857 can be separated into at least two surfaces of the metal substrate (the first layer is opposite to the second layer). The surface of the first layer and the surface of the first layer opposite to the second layer is divided into a coating layer composed of alpha oxide scale 3. Thereby, it is different from the case where the coating layer is formed on only the surface of the metal substrate, and the surface of the metal substrate having the coating layer is on/closed by 3 layers. The metal substrate is composed of an airtight material composed of a first layer, a second layer, and a third layer. Preferably, the material contains Ni and the third layer is composed of an alloy. :===================================================================================================== The overall thermal expansion of the material m ρ = the thermal energy _ coefficient of the glass material composed of the joint cover into the layer and the 苐 3 layer are composed of 42% by mass of the heart, the fish ^ only the people of Berry 4 The 6th alloy is composed of a 6-layer alloy, and the second layer is made of a bismuth alloy containing ", and is made of Fe". The m2 layer and the third layer of the metal substrate are composed of % of the composition. The composition of the alloy can confirm the layer and the coefficient of service. Therefore, the metal base: the number of layers can be close to the thermal expansion coefficient of 100142851 θ 201238857 which is composed of a glass material with a small thermal expansion coefficient. The third layer is composed of 42 masses.

Ni、6質量％之〇、與Fe的一般之^系合金所構成，第2 層為由含有42質量％之见、與以之一般之^系合金所構 成，藉此可使用容易取得的Fe系合金，於對應至接合層所 形成之區域的金屬基材表面上形成由Cr氧化皮膜所構成的 被覆層’且使金屬基材之熱膨㈣數接近由朗材料所構成 之接合層的熱膨脹係數。 上述第1層及第3層為由Fe系合金所構成的氣密密封用 ^材中，較㈣第1層與第3層的合計厚度為金屬基材整體 ^度的5G/〇以上。若為此種構成，則可構成為使接合層之熱 膨脹係數αΐ血今屬且从 . 15 7< ，、金屬基材之熱膨脹係數α2確實滿足 材料所椹？21必10·7的關係，故可確實抑制在由玻璃 二=之接合層中發生破裂的情形。又，本案發明者已 針對此點藉實驗完成確認。 封用蓋姑之第2發明之電子零件收納用盒’係具備：氣密密 被覆層，^包含:金屬基材，係具有至少含&之金屬材料； 構成.他4於金屬基材之表面上，由&之氧化皮膜所 層，係、形成於被覆層之表面上，*不含別之 斤構成’與電子零件收納構材，係經由接合層而與 =被覆層之金屬基材接合，且_ 於 收納電子零件。 本發明第2發明之電子零件收納用盒中，係如上述般，使 100142851 201238857 氣密密封用蓋材含有形成於金屬基材表面上且由Cr之氧化 皮膜所構成的被覆層’與形成於被覆層表面上且由不含％ 之玻璃材料所構成之接合層，而且電子零件收納 為經由接合層而與形成有被覆層之金屬基材接合，故可使構 成被覆層之Cr氧化㈣、與構成接合層之朗材料充分密 黏’而可使金屬基材與電子零件收納構材充分接合。藉此， 可使用不含Pb之玻璃材料，而充分確保電子零件收納用盒 之氣密性。又，由於氣密密封用蓋材含有具金屬材料(其至 少含Cr)之金屬基材’故相較於在基材中使用有㈣材料的Ni, 6 mass% of yttrium, and general alloy of Fe, and the second layer is composed of 42% by mass and a general alloy, whereby Fe can be easily obtained. The alloy is formed on the surface of the metal substrate corresponding to the region where the bonding layer is formed to form a coating layer composed of a Cr oxide film, and the thermal expansion coefficient of the metal substrate is close to the thermal expansion coefficient of the bonding layer composed of the Lang material. . In the hermetic sealing material composed of the Fe-based alloy, the total thickness of the first layer and the third layer is 5 G/〇 or more of the total thickness of the metal substrate. According to this configuration, it is possible to make the thermal expansion coefficient α of the bonding layer and the thermal expansion coefficient α2 of the metal substrate satisfy the material. Since the relationship between 21 and 10 is necessary, it is possible to surely suppress the occurrence of cracking in the bonding layer made of glass. Moreover, the inventor of the present invention has completed the confirmation by the experiment for this point. The electronic component storage case of the second invention of the second aspect of the invention includes: an airtight and dense coating layer, comprising: a metal substrate having a metal material containing at least & a composition; On the surface, the oxide film of the & is formed on the surface of the coating layer, and * does not contain any other components. The electronic component storage member is a metal substrate through the bonding layer and the coating layer. Engage, and _ to accommodate electronic parts. In the electronic component storage case according to the second aspect of the present invention, as described above, the cover member for hermetic sealing of 100142851 201238857 includes a coating layer ' formed of an oxide film of Cr formed on the surface of the metal substrate and formed thereon. a bonding layer made of a glass material containing no % on the surface of the coating layer, and the electronic component is housed to be bonded to the metal substrate on which the coating layer is formed via the bonding layer, so that the Cr constituting the coating layer can be oxidized (four) and The material constituting the bonding layer is sufficiently densely bonded to allow the metal substrate to be sufficiently bonded to the electronic component storage member. Thereby, the glass material containing no Pb can be used, and the airtightness of the electronic component storage case can be sufficiently ensured. Further, since the lid member for hermetic sealing contains a metal substrate having a metal material (which contains at least Cr), it is compared with the material used in the substrate.

If況其可減小氣密密封用蓋材之厚度，故可抑制電子零件 收、”内用皿之大型化。又，藉由使金屬基材具有至少含&的 金屬材料，則可容易於金屬基材表面上形成由^氧化皮膜 所構成的被覆層。 上述第2發明之電子零件收納用盒中，較佳係構成為於 30 C以上且250°C以下的溫度範圍中，接合層之熱膨脹係數 al(/ C)與電子零件收納構材之熱膨脹係數a3(/°c)滿足 OSctl —α3$ l〇xi〇_7的關係。若為此種構成，則在由將接合 層與電子零件收納構材接合時之溫度起降低溫度時，可使在 由玻璃材料所構成之接合層中所發生的應力減小，故可抑制 在由玻璃材料所構成之接合層中發生破裂（裂痕）的情形。 此時’ #父佳係構成為於3〇。〇以上且250。(：以下的溫度範圍 中’接合層之熱膨脹係數α1(/<^)與電子零件收納構材之熱 100142851 ,, 201238857 膨脹係數ot3(/°C)滿足〇Sal —oi3Sl〇xi0-7的關係，且接人 層之熱膨脹係數ai(/°c)與金屬基材之熱膨脹係數a2(rc) = 足·15χ1〇-?$α2 —alS5xl0·7的關係。若為此種構成，則因 OSal —α3$ 1〇χΐ(Γ7 ’故構成為於接合層之電子裳件收納籌 材側不施加應力、或稍微施加拉伸應力。 务 ，孝皆由 -15χ10·7$α2—al$5xl〇·7，則可構成為對接合層之金屬基 材側不施加應力、或稍微施加拉伸應力。藉此，即使在對 合層施加應力，於配置在金屬基材與電子零件收納構材之= 的接合層’係由金屬基材與電子零件_構材雙方施加拉二 應力，故與僅由金屬基材及電子零件收納構材之其中一者對 接合層施加拉伸應力的情形相異，其可抑制於接ς層發生= 裂的情形。 θ 本發明第3發明之氣密密封用蓋材的製造方法，係用於由 陶竞材料所構成，並含有用於收納電子零件之電子零件收納 構材之電子零件收納用盒的氣密密封用蓋材之製造方法，盆 具備：於含有至少含a之金屬材料的金屬基材表面上，’使 金屬基材之Cr氧化而形成由Cr之氧化皮膜所構成之被覆層 的步驟，與於被覆層之表面上，形 9 ..,,m 现由不3 Pb之玻璃材料 斤構成，且用於將形成有被覆層之金屬基材與電子零件收柄 構材接合之接合層的步驟。 本發明第3發明之氣密密封用蓋材之製造方法中 述般，具備：在含有至少含Cr之金屬 备屬材枓的金屬基材之表 100142851If the thickness of the lid member for hermetic sealing can be reduced, it is possible to suppress the enlargement of the electronic component, and to increase the size of the inner container. Further, by making the metal substrate have a metal material containing at least & A coating layer made of an oxide film is formed on the surface of the metal substrate. The electronic component housing case according to the second aspect of the invention is preferably configured to have a bonding layer in a temperature range of 30 C or more and 250 ° C or less. The thermal expansion coefficient a(/C) and the thermal expansion coefficient a3 (/°c) of the electronic component storage member satisfy the relationship of OSctl - α3$ l〇xi〇_7. If it is such a configuration, the bonding layer and the electron are When the temperature at the time of joining the component storage member is lowered, the stress generated in the bonding layer made of the glass material can be reduced, so that cracking (cracking) in the bonding layer made of the glass material can be suppressed. At this time, the # #父佳系系结构为3〇.〇以上和250. (: In the following temperature range, 'the thermal expansion coefficient α1 of the joint layer (/<^) and the heat of the electronic component storage member 100142851 ,, 201238857 Expansion coefficient ot3 (/ ° C) meets 〇Sa l —oi3Sl〇xi0-7 relationship, and the thermal expansion coefficient ai(/°c) of the access layer is related to the thermal expansion coefficient a2(rc) of the metal substrate=foot·15χ1〇-?$α2_alS5xl0·7. According to this configuration, since OSal - α3$ 1 〇χΐ (Γ7 ', it is configured such that no stress is applied to the side of the electronic component of the bonding layer, or a tensile stress is slightly applied. 7$α2—al$5xl〇·7, it is possible to apply no stress to the metal substrate side of the bonding layer or to apply a tensile stress slightly. Therefore, even if stress is applied to the bonding layer, it is disposed in the metal. The bonding layer of the substrate and the electronic component storage member is bonded by the metal substrate and the electronic component to the member, so that the bonding is performed only by one of the metal substrate and the electronic component housing member. The case where the tensile stress is applied to the layer is different, and it can be suppressed in the case where the joint layer is generated and cracked. θ The method for producing a lid member for hermetic sealing according to the third invention of the present invention is for use in a ceramic composition. And a gas containing an electronic component storage box for accommodating an electronic component storage member of an electronic component In the method for producing a lid member for sealing, the pot includes a step of oxidizing Cr of the metal substrate to form a coating layer composed of an oxide film of Cr on the surface of the metal substrate containing the metal material containing at least a, and On the surface of the coating layer, the steps 9 . . , , m are now composed of a glass material material of 3 Pb, and the bonding layer for bonding the metal substrate on which the coating layer is formed and the electronic component receiving member are bonded. In the method for producing a lid member for hermetic sealing according to a third aspect of the present invention, the method of manufacturing a metal substrate comprising a metal base material containing at least Cr is provided as a table 100142851

S 12 201238857 面上，藉由使金屬基材<Cr氧化而形成由α之氧化皮興所 構成之被覆層的步驟；與於被覆層之表面上，形成由不含 Pb之玻雜料所構成，且詩㈣成有被覆狀金屬基材 /、電子令件收納構材接合之接合層的步驟；故可使構成被覆 層之&氧化賴、與構成接合層之_材料充分密黏，而 可使金屬基材與電子零件_構材充分接合。藉此，可使用 不含Pb =玻璃材料，充分確保電子零件收納用盒之氣密 丨又藉由使用含有金屬材料（其至少含有⑺之金屬基 ^，則相♦較於在基材中使_£材料的情形，其可減小氣密 始、封用盍材之厚度’故可抑制電子零件收納用盒之大型化。 二:Γ金屬基材含有至少含cr的金屬材料，則可容易 上述面上形成由Cr氧化皮膜所構成的被覆層。 上述第3發明之氣密密封用蓋材之製 成被覆層之步驟包含：於含有 Μ b糾 表面上，形成由Cr之氧化皮_構==料的金屬基材 盔士播嫌士 T構成之被覆層的步驟。若 crmr藉由使金屬基材為由含有上之 Cr的Fe糸δ金所構成，則可於 。氧化皮膜所構成之被覆層。又屬=面上確實形成由 有6質量％以下之Cr的Fe系人八糟{金屬基材為由含 之過剩含量而金屬基材之熱膨八則可抑制因Cr 脹係數與接合層之熱膨脹係數顯著不同的 100142851 201238857 制因熱膨脹差異所造成之破裂（裂痕）等發生於接合層或金 屬基材的情形。又，藉由使金屬基材含有Ni，則可減小金 屬基材之熱膨脹純，故可使金屬基狀_祕數更加接 近由熱膨脹係數小於金屬⑽之玻璃材料所構成之接合層 的熱膨脹係數。 此時，較佳係形成由Cr氧化皮膜所構成之被覆層的步 驟，具有：在濕潤氫氣環境下，且1〇〇〇χ：以上、⑴代以 下的溫度條件T，使金屬基材之〇優先地，藉此於金 屬基材表©上’優先形成由Cr之氧化皮騎構叙被覆層 的步驟。若為此種構成，則可確實地充分確保由Cr之氧化 皮膜所構成之被覆層的厚度。 上述具有優先形成由Cr之氧化皮膜所構成之被覆層之步 驟的氣㈣封用蓋材之製造方法+，餘係優先形成由& 之氧化皮膜所構成之被覆層的步驟，具有：在將氧分壓設定 為小於可將Fe及Ni氧化之分壓、且大於可將&氧化之分 壓的濕潤氫氣環境下，優先形成由Cr之氧化皮膜所構成: 被覆層的步驟。若為此種構成，可容易僅使Cr優先被氧化， 故可更確實地於金屬基材表面上充分確保由Cr之氧化皮膜 所構成之被覆層的厚度。 【實施方式】 以下，根據圖式說明將本發明具體化之實施形雜。 (第1實施形態） 100142851 14 201238857 首先’參照圖1刀闻〇 圖2，說明本發明第1實施形態之氣密 密封用蓋材1的構造。 第1實施形態之¥ + 、 之虱费密封用蓋材1係如圖1所示，由蓋 10、與形成於蓋1〇上 上面10a上(Z1側表面上）的玻璃層u 所形成。蓋10係由表γ +二 > 方向上具有約2.4mm長度L1、於 Y方向上具有約19 τ又 ^ ... 長度L2及於Z方向上具有約o.imm 尽度tl的直方體所槿 « .成。又，玻璃層11為本發明之「接合 層」的一例。 玻璃層11係形成為沿 考'盖· 1〇上面10a之端部g办士曰isi 的寬度W(轉圖2)， 以#大致相门 此玻璃層η係依對…向具有約〇.〇5_之厚度t2。 32之上面32a(參照圖^電子零件收納構们〇之框體 形成為框狀。，的方式’沿著^上面⑽之端部 另外’玻璃層11係冬右·士 不含Pb之V系低融马 構=〇5姆_所構成的 點玻璃的鮮摄係數α1，脉H翻層1丨之v系低融On the surface of S 12 201238857, a step of forming a coating layer composed of oxidized skin of α by oxidizing a metal substrate <Cr; and forming a glass porridge containing no Pb on the surface of the coating layer And the poem (4) is a step of forming a bonding layer in which the covering metal substrate/the electronic component housing member is joined; therefore, the oxide layer constituting the coating layer and the material constituting the bonding layer can be sufficiently adhered. The metal substrate can be sufficiently bonded to the electronic component. Thereby, the Pb=glass-free material can be used, and the airtightness of the electronic component storage case can be sufficiently ensured, and by using the metal-containing material (which contains at least the metal base of (7), the phase ♦ is made in the substrate In the case of the material, the thickness of the airtight starter and the sealing material can be reduced, so that the enlargement of the electronic component storage case can be suppressed. Second, the base metal substrate contains a metal material containing at least cr, which is easy to be used. A coating layer made of a Cr oxide film is formed on the surface. The step of forming the coating layer for the hermetic sealing lid member according to the third aspect of the invention includes forming an oxide scale of Cr on the surface containing the crucible The step of forming a coating layer of the metal substrate of the material of the material of the material, and the composition of the metal substrate is made of Fe 糸 δ gold containing the upper Cr, and the oxidized film is formed. The coating layer is also formed on the surface of the Fe-based hexahedron with a mass of 6 mass% or less. {The metal substrate is composed of a super-containing content and the thermal expansion of the metal substrate can suppress the coefficient of expansion due to Cr. The coefficient of thermal expansion of the joint layer is significantly different 100142851 201238857 The crack (crack) caused by the difference in thermal expansion occurs in the case of the bonding layer or the metal substrate. Further, by making the metal substrate contain Ni, the thermal expansion of the metal substrate can be reduced, so that the metal base can be made. The secret number is closer to the thermal expansion coefficient of the bonding layer composed of the glass material having a thermal expansion coefficient smaller than that of the metal (10). In this case, the step of forming the coating layer composed of the Cr oxide film is preferably performed in a humid hydrogen atmosphere, and 1〇〇〇χ: The temperature condition T of the above (1) generation or less makes the enthalpy of the metal substrate preferentially, thereby preferentially forming a step of forming a coating layer from the scale of Cr on the metal substrate surface. According to this configuration, the thickness of the coating layer composed of the oxide film of Cr can be surely ensured. The manufacture of the gas (four) sealing lid member having the step of preferentially forming the coating layer composed of the oxide film of Cr is preferable. Method +, the step of preferentially forming a coating layer composed of an oxide film of & has a partial pressure of oxygen set to be smaller than a partial pressure at which Fe and Ni can be oxidized, and greater than that which can be oxidized In the humidified hydrogen atmosphere under pressure, the step of forming a coating layer of Cr oxide film is preferentially formed. With such a configuration, it is easy to preferentially oxidize only Cr, so that it can be sufficiently ensured on the surface of the metal substrate. The thickness of the coating layer composed of the oxide film of Cr. [Embodiment] Hereinafter, the embodiment of the present invention will be described with reference to the drawings. (First embodiment) 100142851 14 201238857 First, 'refer to FIG. Fig. 2 is a view showing the structure of the lid member 1 for hermetic sealing according to the first embodiment of the present invention. The lid member 1 for the sealing of the first embodiment is as shown in Fig. 1, and is formed by the lid 10 and The glass layer u is formed on the upper surface 10a (on the Z1 side surface) of the lid 1 . The cover 10 has a length L1 of about 2.4 mm in the direction of the table γ + two > a length L1 of about 19 τ in the Y direction, and a length L2 of about o.imm in the Z direction. The 槿«. Further, the glass layer 11 is an example of the "joining layer" of the present invention. The glass layer 11 is formed so as to be along the width of the end portion 10a of the top cover 10a, and the width W (Fig. 2) of the sapphire ii is the same as that of the glass layer η. 〇5_ thickness t2. 32's upper surface 32a (refer to the figure ^Electronic parts storage structure, the frame is formed into a frame shape. The way 'is along the end of the upper surface (10). 'The glass layer 11 is the right side of the line. The horse-forming structure = 〇5 m _ is composed of the fresh-keeping coefficient α1 of the point glass, and the pulse H is layered.

S 之溫度範圍，構成為約7GxlG_7/<t。X上且、力25〇c以下 構成為玻璃轉移點為約285它。又又，V系低融點破璃係 V系低融點玻璃之_脹倾急遽變^^璃轉移點’係指 以上之溫度範圍中的熱膨脹係數（的酿^ 玻螭轉移點 璃轉移點以下之溫度範園140xlo7/c)亦大於破 •urn：)。又，構成玻璃層的熱膨服係數α1(約 _侧 ^低融點料之密封 15 201238857 溫度係構成為約370°C以上且約400°C以下。 另外，構成玻璃層11之V系低融點玻璃係構成為抑制水 分子侵入至結晶構造内部。藉此，玻璃層11具有耐濕性（耐 水性）。 蓋10係如圖2所示，由金屬基材12、與形成為包圍金屬 基材12之約整面的氧化皮膜層13所構成。於此氧化皮膜層 13上面上形成有玻璃層11。又，金屬基材12係由含有約 42質量％之Ni、約2質量％以上且約6質量％以下之Cr、 與Fe的Fe系合金(42Ni-(2〜6)Cr-Fe合金)所構成。又，金屬 基材12較佳係由含有約3質量％以上且約6質量％以下之 Cr的Fe系合金(42Ni-(3〜6)Cr-Fe合金)所構成。又，氧化皮 膜層13為本發明之「被覆層」之一例。 於此，第1實施形態中，較佳係於約30°C以上且約250°C 以下之溫度範圍中，構成金屬基材12之F e系合金之熱膨脹 係數α2為約55xlO_7/°C以上且約75xlO_7/°C以下。亦即，較 佳係於約30°C以上且約250°C以下之溫度範圍中，玻璃層 11之熱膨脹係數αΐ與金屬基材12之熱膨脹係數α2滿足 15x1(T7S(x2—α1^5χ10_7的關係。其結果，於約30°C以上 且約250°C以下之溫度範圍中，玻璃層11與金屬基材12不 易發生因熱膨脹差異所造成的應力。 另外，第1實施形態中，氧化皮膜層13主要由Cr203之 皮膜所構成，且於Z方向上具有約0.3μτη以上且約1.2μιηThe temperature range of S is composed of about 7GxlG_7/<t. On X, the force is 25 〇c or less, and the glass transition point is about 285. In addition, the V-based low-melting point-breaking glass system V-based low-melting point glass _ swell-thrusting 遽 ^ ^ ^ ^ 转移 ^ 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 以上 以上 以上 以上 以上 以上The temperature of the Fan Park 140xlo7/c) is also greater than the break•urn:). Further, the thermal expansion coefficient α1 of the glass layer (about _ side ^ low melting point seal 15 201238857 temperature system is formed to be about 370 ° C or more and about 400 ° C or less. In addition, the V layer constituting the glass layer 11 is low. The melting point glass is configured to suppress entry of water molecules into the crystal structure. Thereby, the glass layer 11 has moisture resistance (water resistance). The lid 10 is formed of a metal substrate 12 and surrounded by a metal as shown in FIG. 2 . The oxide film layer 13 is formed on the entire surface of the substrate 12. The glass layer 11 is formed on the upper surface of the oxide film layer 13. Further, the metal substrate 12 contains about 42% by mass of Ni and about 2% by mass or more. Further, it is composed of about 6% by mass or less of Cr and a Fe-based alloy of Fe (42Ni-(2 to 6)Cr-Fe alloy). Further, the metal base material 12 preferably contains about 3% by mass or more and about 6 An Fe-based alloy (42Ni-(3~6)Cr-Fe alloy) having a mass % or less of Cr. The oxide film layer 13 is an example of the "coating layer" of the present invention. Here, in the first embodiment, Preferably, the thermal expansion coefficient α2 of the Fe alloy constituting the metal substrate 12 is in a temperature range of about 30 ° C or more and about 250 ° C or less. It is about 55×10 −7 /° C. and about 75×10 −7 /° C. or less, that is, preferably in a temperature range of about 30° C. or higher and about 250° C. or lower, the thermal expansion coefficient α ΐ of the glass layer 11 and the metal substrate 12 . The coefficient of thermal expansion α2 satisfies the relationship of 15x1 (T7S(x2—α1^5χ10_7. As a result, in the temperature range of about 30° C. or more and about 250° C. or less, the glass layer 11 and the metal substrate 12 are less likely to be different in thermal expansion. In addition, in the first embodiment, the oxide film layer 13 is mainly composed of a film of Cr203, and has a thickness of about 0.3 μτη or more and about 1.2 μm in the Z direction.

100142851 16 S 201238857 以下的厚度t3。另外，氧化皮膜層13係藉由使金屬基材12 之Fe系合金所含有之Cr於金屬基材12表面上進行氧化而 形成。 其次，參照圖3及圖4，說明本發明第1實施形態之氣密 密封用蓋材1所使用之電子零件收納用盒100的構造。 第1實施形態之電子零件收納用盒100係如圖3及圖4 所示般，具有使收納了水晶振盪器20(參照圖4)之電子零件 收納構材30被上述氣密密封用蓋材1之玻璃層11所密封的 構造。此時，氣密密封用蓋材1係配置成氣密密封用蓋材1 之蓋10之上面10a為下側（Z3側）。又，水晶振盪器20為本 發明之「電子零件」之一例。 電子零件收納構材30係由屬於陶瓷材料之Al2〇3所構 成，且由平面觀看時，於X方向具有約2.5mm之長度L3 及於Y方向上具有約2.0mm之長度L4。又，電子零件收納 構材30係因由陶瓷材料所構成，故具有絕緣性。又，於約 30°C以上且約250°C以下之溫度範圍中，構成電子零件收納 構材30之Al2〇3之熱膨脹係數α3為約65xl(T7/°C。亦即， 構成為於約30°C以上且約250°C以下之溫度範圍中，玻璃層 11之熱膨脹係數αΐ(約7〇xl(T7/°C)與電子零件收納構材30 之熱膨脹係數α3滿足0^α1_α3(=約5xl0_7)S10xl(T7的關 係。其結果，於約30°C以上且約250°C以下之溫度範圍中， 玻璃層11與電子零件收納構材3 0不易發生因熱膨脹差異所 100142851 17 201238857 造成的應力。 卜電子零件收納構材3〇係如圖4所示般，包括〇 "之底31、與形成為由底部3!上面(Z4側之面）周圍朝 Ζ4方向延伸的框部32。又，電子零件收納構材30中，係 因被底部31及框體32所包圍而形成凹部33。此凹部33係 I成為於上方(Ζ4側）具有開口部，藉由於凹部％中之底部 面(Ζ4側之面）上經由凸塊4〇安裝水晶振盛器如，而使 水晶振盪器20收納於凹部33中。 另外，氣密密封用蓋材1之蓋1〇，係經由玻璃層1卜接 =於電子零件收納構材3G之框體％之上面他。具體而 言’經融解之氣料封用蓋材1之玻璃層u，係藉由依配 置於框體32上面仏之狀態被冷卻，而使氣密㈣用蓋材 1之蓋10與電子零件收納構材30接合。藉此，密封電子零 件收納用盒100。於此，由收納了水晶振I器⑼之電子零 件收納構材3G的凹部33、氣密密封用蓋材1之蓋1()、與玻 璃f 11所構成的空間，係構成為具有氣密性的狀態(略真空 狀I、）藉此’可抑制水晶振盤器20中之振動特性等改 化）。 另外，上述金屬基材12之熱膨脹係數CX2係根據電子零件 收、内構材30之熱膨脹係數α3與玻璃層丨丨之熱膨脹係數以 的關係而規定。亦即，由於玻璃層U之熱膨脹係數α1為電 子零件收納構材30之熱膨脹係數α3以上，故於玻璃層η 100142851 201238857 之電子零件收納構材30側並不施加應力、或稍微施加拉伸 應力。於此，藉由依使金屬基材12之熱膨脹係數α2滿足 -15χ10·7$α2 —α1$5χ1(Τ7之關係的方式構成金屬基板12， 而可構成為於玻璃層11之蓋丨〇側並不施加應力、或稍微施 加拉伸應力。其結果，即使是對玻璃層11施加應力的情況， 由於對配置於蓋1〇與電子零件收納構材30之間的玻璃層 11，由蓋10與電子零件收納構材30雙方施加拉伸應力，故 即使是由對拉伸應力容易發生破裂（裂痕）的V系低融點玻 璃所構成的玻璃層I1 ’即可使其不易發生破裂。 接著，參照圖1〜圖6，說明第1實施形態之電子零件收納 用盒100的製造製程。 首先，準備圖1及圖2所示之由42Ni-(2〜6)Cr-Fe合金所 構成的金屬基材12。然後’如圖5所示般，對金屬基材12， 於露點為約30°C之濕潤氫氣環境中，且約900°C以上約 1150X：以下的溫度條件下’進行約30分鐘的氧化處理(Cr 優先乳化）。又’溫度條件較佳為約l〇〇〇°C以上且約1150°C 以下。此時，由於氫氣之露點為約3(rc，故濕潤氫氣環境 内之氧分壓小於可使Fe及Ni氧化之分壓，另一方面，大於 可將Cr氧化的分壓。藉此，於金屬基材12表面上，可不使 Fe及Ni氧化而僅使Cr被優先氧化。其結果，主要由& 〇 所構成、具有約〇.3μιη以上且約1.2μιη以下之厚度t3(來照 圖2)的氧化皮膜層π，形成於金屬基材12的約整面上。 100142851 ,〇 201238857 然後，如圖！及圖2所示般，沿著氧化皮膜 1〇之上面心)’於氧化皮獏層13上面塗佈;含3 :上面(蓋 低融點玻璃之糊料。其後，於約4HTC之溫度條件之V系 、藉此去除V系低融點玻璃之糊料内的 、订境 製造沿著蓋!。上面iOa之端部形成有玻璃層：二藉此， 用蓋材1。 的乳密密封 另外，如® 4所示般，準備於凹部33收納有水 2〇的電子零件收蚋爐姑μ L 日日振盪器 玻# u㈣t ，錢密密_蓋材k 玻璃層11位於電子零件收納構材3〇之框體32 之 1 3〇ι^ 圖6所不般，依將氣密密封用蓋材1配置於曾二 件收納構材30的狀態载置於真空爐2内，於真空狀零 贿以上⑽W度條件下，使梅約 、其後’藉由將氣密密封用蓋材1及電子零件收納構材30 冷部如圖4所示般’經由玻璃層u，使氣密密封用蓋材1 之蓋丨〇接合於電子零件收納構材3〇之框體32上面Ua。 於此’在氣密密封用蓋材丨之蓋1G與電子零件收納構材3。〇 開始接合之固黏溫度（約取C)起至構成玻璃層u之V系 低融點麵之玻璃轉移點（約285t)為止的溫度範圍（破璃 轉移點Μ上之溫度範圍）内，相較於金屬基材12之熱膨服係 數α2(約55x10 7/eC以上且約mmoYc以下）及電子零件收 納構材30之熱膨脹係數幻（約65xl〇_7/<t)，玻璃層u之熱 100142851 20 201238857 膨脹係數（約14〇xl(T7/°C)較大。然而，在玻璃轉移點以上之 溫度範圍中由於玻璃層11具有流動性，故於蓋1〇(金屬基 材12)、玻璃層11及電子零件收納構材30中，不致發生因 熱膨脹係數差異所造成的應力。又，在玻璃轉移點以下之溫 度範圍（約30°C以上且約250°C以下之溫度範圍）中，由於使 玻璃層11與蓋10及電子零件收納構材30構成為不易發生 因熱膨脹差異所造成的應力，故冷卻後，累積於蓋10、玻 璃層11及電子零件收納構材30的應力較小。 另外，由於在真空狀態下進行接合（密封），而使由收納有 水晶振盪器20之電子零件收納構材30之凹部33、氣密密 封用蓋材1之蓋10、與玻璃層11所構成的空間，成為具有 充分氣密性的狀態（略真空狀態）。又，為了使由凹部33與 蓋10與玻璃層11所構成之空間密封成更確實具有氣密性的 狀態，較佳係於約380°C以上之溫度條件下使玻璃層11融 解而進行密封。又，藉由於約400°C以下之溫度條件下使玻 璃層11融解而進行密封，則可減小密封時熱對水晶振盪器 20的影響。如此，製造圖3所示之經氣密密封的電子零件 收納用盒100。 第1實施形態中，如上述般，氣密密封用蓋材1係具備形 成於金屬基材12表面上之主要由Cr203皮膜所構成的氧化 皮膜層13、與形成於氧化皮膜層13表面上之具有由 V2〇5_P2〇5_TeO-Fe2〇3所構成之不含Pb之V糸低融點玻璃 100142851 21 201238857 的玻璃層11，藉此可使構成氧化皮膜層13iCr2〇3皮膜、 與構成玻璃層11之V系低融點玻璃充分密黏，故可使金屬 基材12與電子零件收納構材30充分接合。藉此，使用不含 Pb之V系低融點玻璃，可充分確保電子零件收納用盒 之氣密性。又，藉由使氣密密封用蓋材丨具備由 42Ni-(2〜6)Cr-Fe合金所構成的金屬基材12，則相較於在基 材中使用有陶瓷材料的情況，可減小氣密密封用蓋材丨之厚 度tl，故可抑制電子零件收納用盒1〇〇的大型化。又，藉由 使金屬基材12為由42Ni-(2〜6)Cr-Fe合金所構成，則可容易 於金屬基材12表面上形成由〇2〇3所構成的氧化皮膜層13。 另外，第1實施形態申，如上述般，由於構成為在約3〇它 以上且約25(TC以下之溫度範圍中，玻璃層u之熱膨脹係 數Oil與金屬基材12之熱膨脹係數α2滿足_15χ1〇_7$α2 — alS5xl(T7的關係，故在由將金屬基材12與玻璃層u接合 時之溫度進行降溫時，可減小在由V系低融點玻璃所構成 之玻璃層11所發生的應力’故可抑制在由v系、低融點玻璃 所構成之玻璃層11發生破裂（裂痕）β x，藉由構成為使玻 璃層11之熱膨脹係數α1與金屬基材12之熱膨脹係數α2 滿足-15χ10、α2-α1的關係，則可抑制相較於壓縮應力而 更各易對拉伸應力發生破裂、對構成破璃層u之ν系低融 點玻璃所施加的拉伸應力變得過大的情形。 另外’第1實施形態中’如上述般’藉由使氧化皮膜層 100142851100142851 16 S 201238857 The following thickness t3. Further, 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 housing case 100 used in the hermetic sealing cover member 1 according to the first embodiment of the present invention will be described with reference to Fig. 3 and Fig. 4 . As shown in FIG. 3 and FIG. 4, the electronic component storage case 100 of the first embodiment has the electronic component storage member 30 in which the crystal oscillator 20 (see FIG. 4) is housed, and the cover member for hermetic sealing. The structure in which the glass layer 11 of 1 is sealed. At this time, the lid member 1 for hermetic sealing is disposed such that the upper surface 10a of the lid 10 of the lid member for hermetic sealing is the lower side (Z3 side). Further, the crystal oscillator 20 is an example of the "electronic component" of the present invention. The electronic component storage member 30 is made of Al2〇3 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. Further, since the electronic component housing member 30 is made of a ceramic material, it has insulation properties. Further, in a temperature range of about 30 ° C or more and about 250 ° C or less, the thermal expansion coefficient α3 of Al 2 〇 3 constituting the electronic component housing member 30 is about 65 x 1 (T7 / ° C. That is, it is configured to be about In the temperature range of 30 ° C or more and about 250 ° C or less, the thermal expansion coefficient α ΐ (about 7 〇 x 1 (T7 / ° C) of the glass layer 11 and the thermal expansion coefficient α3 of the electronic component storage member 30 satisfy 0^α1_α3 (= About 5xl0_7) S10xl (T7 relationship. As a result, in the temperature range of about 30 ° C or more and about 250 ° C or less, the glass layer 11 and the electronic component storage member 30 are less likely to be caused by the difference in thermal expansion, 100142851 17 201238857 As shown in Fig. 4, the electronic component storage member 3 includes a bottom portion 31 and a frame portion 32 which is formed to extend in the direction of the crucible 4 from the periphery of the bottom portion 3! (the surface on the Z4 side). Further, in the electronic component housing member 30, the concave portion 33 is formed by being surrounded by the bottom portion 31 and the frame body 32. The concave portion 33 is formed to have an opening portion on the upper side (the side of the crucible 4), and the bottom portion of the recess portion is On the surface (the side of the Ζ4 side), the crystal vibrator is mounted via the bump 4, and the crystal oscillator 20 is received. The cover 1 of the hermetic sealing cover material 1 is connected to the upper surface of the frame body of the electronic component storage member 3G via the glass layer 1. Specifically, it is melted. The glass layer u of the gas material sealing cover material 1 is cooled in a state of being placed on the upper surface of the frame body 32, and the lid 10 of the lid member 1 for airtightness (4) is joined to the electronic component storage member 30. The electronic component storage case 100 is sealed. The recessed portion 33 of the electronic component housing member 3G in which the crystal oscillator (9) is housed, the cover 1 () of the hermetic sealing cover member 1 and the glass f 11 are formed. The space is configured to be airtight (slightly vacuumed I), thereby suppressing the vibration characteristics and the like in the crystal disk unit 20. The thermal expansion coefficient CX2 of the metal substrate 12 is also According to the relationship between the thermal expansion coefficient α3 of the electronic component 30 and the thermal expansion coefficient of the glass layer 。, that is, the thermal expansion coefficient α1 of the glass layer U is equal to or higher than the thermal expansion coefficient α3 of the electronic component storage member 30. Therefore, the electronic parts of the glass layer η 100142851 201238857 The member 30 does not apply stress or slightly exerts tensile stress. Here, the metal substrate is formed in such a manner that the thermal expansion coefficient α2 of the metal substrate 12 satisfies the relationship of -15χ10·7$α2 — α1$5χ1 (Τ7). 12, the stress can be applied to the lid side of the glass layer 11, or a tensile stress is slightly applied. As a result, even if stress is applied to the glass layer 11, the pair is placed on the lid 1 and the electrons. Since the glass layer 11 between the component storage members 30 is subjected to tensile stress by both the cover 10 and the electronic component storage member 30, even the V-based low-melting glass which is likely to be cracked (cracked) by tensile stress is used. The glass layer I1' formed can be made less susceptible to cracking. Next, a manufacturing process of the electronic component housing case 100 according to the first embodiment will be described with reference to Figs. 1 to 6 . First, a metal base material 12 composed of a 42Ni-(2 to 6)Cr-Fe alloy as shown in Figs. 1 and 2 is prepared. Then, as shown in FIG. 5, the metal substrate 12 is subjected to oxidation treatment for about 30 minutes in a humid hydrogen atmosphere having a dew point of about 30 ° C and at a temperature of about 900 ° C or higher and about 1150 X: or less. (Cr preferentially emulsified). Further, the temperature condition is preferably about 10 ° C or more and about 1150 ° C or less. At this time, since the dew point of hydrogen is about 3 (rc, the partial pressure of oxygen in the humidified hydrogen atmosphere is smaller than the partial pressure at which Fe and Ni can be oxidized, and on the other hand, is greater than the partial pressure at which Cr can be oxidized. On the surface of the metal substrate 12, only Cr can be preferentially oxidized without oxidizing Fe and Ni. As a result, it is mainly composed of & 、, and has a thickness t3 of about 0.3 μm or more and about 1.2 μm or less. 2) The oxide film layer π is formed on the entire surface of the metal substrate 12. 100142851, 〇201238857 Then, as shown in Fig. 2 and Fig. 2, along the upper surface of the oxide film 1) Coating on the top layer 13; containing 3: top (covering the paste of the low melting point glass. Thereafter, in the V system at a temperature of about 4HTC, thereby removing the paste in the V-based low melting point glass, Manufactured along the cover! The upper part of the iOa is formed with a glass layer: by this, the nipple seal of the cover material 1 is used, and as shown in Fig. 4, the electrons prepared for the water in the recess 33 are prepared. Parts Reclamation Furnace μ L 日 日 Oscillator Glass # u(四)t , Qian Mi Mi _ cover material k Glass layer 11 is located in the electronic parts storage material 3 In the case of the two-piece storage member 30, the cover member 1 for the hermetic sealing is placed in the vacuum furnace 2, and the vacuum is less than one bribe. (10) Under the condition of W degree, the lid member for hermetic sealing is passed through the glass layer u by the sealing member 1 for the hermetic sealing and the cold portion of the electronic component housing member 30 as shown in Fig. 4 The cover of 1 is joined to the upper surface Ua of the frame 32 of the electronic component storage member 3, and the cover 1G for the hermetic sealing cover member and the electronic component storage member 3 are used. (About C) The temperature range (temperature range on the glass transition point 构成) of the glass transition point (about 285t) of the V-based low melting point surface of the glass layer u is compared with the metal substrate 12 The thermal expansion coefficient α2 (about 55x10 7 / eC or more and about mmoYc or less) and the thermal expansion coefficient of the electronic component storage member 30 (about 65xl 〇 _7 / < t), the heat of the glass layer u 100142851 20 201238857 expansion The coefficient (about 14 〇 xl (T7 / ° C) is large. However, in the temperature range above the glass transition point, since the glass layer 11 has fluidity, In the cover 1 (metal substrate 12), the glass layer 11, and the electronic component storage member 30, stress due to the difference in thermal expansion coefficient does not occur, and the temperature range below the glass transition point (about 30 ° C or higher and In the temperature range of about 250 ° C or less, the glass layer 11 and the lid 10 and the electronic component housing member 30 are configured to be less susceptible to stress due to the difference in thermal expansion, so that they are accumulated in the lid 10 and the glass layer 11 after cooling. The stress of the electronic component storage member 30 is small. In addition, since the recessed portion 33 of the electronic component housing member 30 in which the crystal oscillator 20 is housed, the lid 10 for the hermetic sealing lid member 1, and the glass layer 11 are formed by bonding (sealing) in a vacuum state. The space becomes a state with sufficient airtightness (slightly vacuumed state). Further, in order to seal the space formed by the recessed portion 33 and the lid 10 and the glass layer 11 to be more airtight, it is preferable to melt the glass layer 11 at a temperature of about 380 ° C or higher and seal it. . Further, by sealing the glass layer 11 under the temperature of about 400 ° C or lower, the effect of heat on the crystal oscillator 20 during sealing can be reduced. Thus, the hermetically sealed electronic component housing case 100 shown in Fig. 3 was produced. In the first embodiment, the lid member 1 for hermetic sealing includes the oxide film layer 13 mainly composed of a Cr203 film formed on the surface of the metal substrate 12, and the surface of the oxide film layer 13 formed on the surface of the oxide film layer 13. A glass layer 11 having a Pb-free V 糸 low melting point glass 100142851 21 201238857 composed of V2〇5_P2〇5_TeO-Fe2〇3, whereby the oxide film layer 13iCr2〇3 film and the glass layer 11 can be formed. Since the V-based low-melting point glass is sufficiently dense, the metal base material 12 and the electronic component storage member 30 can be sufficiently joined. As a result, the V-based low-melting glass containing no Pb can be used to sufficiently ensure the airtightness of the electronic component storage case. Further, when the lid member for hermetic sealing is provided with the metal base material 12 made of a 42Ni-(2 to 6)Cr-Fe alloy, it can be reduced as compared with the case where a ceramic material is used for the base material. Since the thickness tl of the lid member for small airtight sealing is tl, it is possible to suppress an increase in size of the electronic component housing case 1 . Further, by forming the metal base material 12 from a 42Ni-(2 to 6)Cr-Fe alloy, the oxide film layer 13 composed of 〇2〇3 can be easily formed on the surface of the metal base material 12. Further, in the first embodiment, as described above, the thermal expansion coefficient of the glass layer u and the thermal expansion coefficient α2 of the metal substrate 12 are satisfied in a temperature range of about 3 Å or more and about 25 (TC or less). 15χ1〇_7$α2 — alS5xl (T7 relationship, when the temperature is lowered when the metal substrate 12 and the glass layer u are joined, the glass layer 11 composed of the V-based low melting point glass can be reduced. The stress generated is such that cracking (cracking) β x in the glass layer 11 composed of the v-based or low-melting glass can be suppressed, and the thermal expansion coefficient α1 of the glass layer 11 and the thermal expansion of the metal substrate 12 are configured. When the coefficient α2 satisfies the relationship of -15χ10 and α2-α1, it is possible to suppress the tensile stress caused by the tensile stress and the tensile stress applied to the ν-based low-melting glass constituting the glazing layer u as compared with the compressive stress. In the case of the first embodiment, as described above, by making the oxide film layer 100142851

22 S 201238857 13之厚度t3 $約〇.3μηι以上且約12MJn以下，則可充分確 保氧化皮膜層13之厚度t3，故可使構成氧化皮膜層U之 2〇3皮膜、與構成玻璃層11之V系低融點玻璃確實密黏。 另外，第1實施形態中，如上述般，藉由構成為使金屬基 材12為由42Ni_(2〜6)Cr-Fe合金所構成，則可於金屬基材 12之約整面上確實形成由C]：2〇3皮膜所構成的氧化皮膜層 13。又，可抑制因Cr過剩含量所造成之金屬基材12之熱膨 脹係數α2變大、金屬基材12之熱膨脹係數α2與玻璃層n 之熱膨脹係數αΐ顯著差異的情形。藉此，可抑制於玻璃層 11或金屬基材12上發生因熱膨脹差異所造成的破裂等。 又，藉由使金屬基材12含有42質量％的Ni，則可減小金屬 基材12的熱膨脹係數α2。藉此，可使金屬基材12之熱膨 脹係數α2更確實接近由熱膨脹係數一般小於金屬材料之ν 系低融點玻璃所構成的玻璃層11的熱膨脹係數α1。豆处 果’可更加抑制於玻璃層Π發生因熱膨脹差異所造成之破 裂專情形。 另外，第1實施形態中，如上述般，藉由構成為金屬基材 12為由42Ni-(3〜6)Cr-Fe合金所構成，則可使破璃層丨丨之 熱膨脹係數αΐ與金屬基材12之熱膨脹係數α2確實滿足 -15 X10 7 ^ α2 — α 1 S 5 X10 7的關係，故可確實抑制在由ν系 低融點玻璃所構成之玻璃層11發生破裂的情形。 另外，第1實施形態中’如上述般’藉由使氧化皮膜層 100142851 23 201238857 13形成為包圍金屬基材 之兩表面之其中—面上 約整面，則與僅在金屬基材12 v成氧化皮膜層13的情 防止將玻彻11錯料·未形财可 基材Π表面上。又，與僅在金屬基材12之—部:=屬 皮膜層13的情況不同，在形 =成氧化 基材12之-部分進㈣| m ^ 130^需對金屬 又，可容㈣絲化皮膜層 13。又’由於使由具有耐純之⑽所構成之氧化皮膜層 !3形成為包圍金屬基材12之約整面，故可提升金屬基材η 的而t #性 另外，第1實施形態中，如上述般，藉由構成為在約3(rc 以上且約25G°C以下的溫度範圍中’玻璃層n之熱膨服係 數αΐ(約70x10 /C)與電子零件收納構材3〇之熱膨脹係數 α3(約 65xl07/°C)滿足 〇$αΐ〜α3(=^ 5xl〇-7)g1〇xl〇-7 的關 係，則在由將玻璃層11與電子零件收納構材3〇接合時之固 黏溫度（約300°C)進行降溫時，可減小在由v系低融點玻璃 所構成之玻璃層11所發生的應力，故可抑制在由V系低融 點玻璃所構成之玻璃層11發生破裂的情形。 另外，第1實施形態中，如上述般，構成為在約3(rca 上且約250°C以下之溫度fe圍中’玻璃層11之熱膨脹係數 αΐ(約70x10 7/C)與電子零件收納構材30之熱膨脹係數 α3(約 65><10力。〇滿足 〇Sal-~cx3(=約 5χ10·7)$ΐ〇χΐ〇-7，且 玻璃層11之熱膨脹係數αΐ與金屬基材12之熱膨脹係數 100142851 24 201238857 α2(約 55xl(T7/°C 以上且約 75xl(T7/°C 以下）4_15χ10-7$α2〜 alShio 。藉此，即使是對玻璃層η施 由於對配置於一與電子零件收納構=:破 2 11 ’由金屬基材12與電子零件收納構材3G雙方施加 拉:應力，故與僅由金屬基材12及電子零件收納構材 之其中一者對玻璃層U施加拉 於玻璃層11發生破裂。 Μ 、月开V不同可抑制 ^卜’第！實施形態中，如上述般，藉由對金屬基材12, 在4點為約30C，小於可將f孩 产 及Nl氣化之分壓、並大於 可將Cr氧化之分壓的濕潤氳氣 、 ㈣Ca下的温度條件下，進^^且約⑽代以上約 之優先氧化），則可容易僅使㈣ MM處理 金屬基材12表面上充分確保由故可更確實地於 膜層13的厚度。 叫皮模所構成的氧化皮 (實施例） 其次，參照圖2及圖7〜圖17， 兄月為了確認第1實施形 悲之效果而進灯的熱祕係數測定及_ (熱膨脹係數測定） “ 以下說明之熱膨脹係數涓彳定，在 '、σ圖7所示般，作為對廄 上述第1實施形態之金屬基材12 作為對應 % ^的實施例丨〜5，於含有 質量％之见與Fe的Fe系合金中 、有 Μϋ。 — G含有率不同的 100142851 25 201238857 具體而言，作為實施例1，使用含有2質量°/〇Cr的Fe系 合金(42Ni-2Cr-Fe合金）。又，作為實施例2，使用含有3質 量％0的Fe系合金(42Ni-3Cr-Fe合金）◊又，作為實施例3， 使用含有4質量％0的Fe系合金(42Ni-4Cr-Fe合金）。又， 作為貫施例4 ’使用含有5質董％Cr的Fe系合金 (42Ni-5Cr-Fe合金）。又，作為實施例5，使用含有6質量 %Cr 的 Fe 系合金(42Ni-6Cr-Fe 合金）。 另一方面，作為相對於實施例1〜5的比較例1，使用含有 42質量。/〇之Ni與Fe，且不含〇的Fe系合金(42Ni-Fe合金）。 另外’作為相對於第1實施形態之金屬基材的參考例1， 使用由構成上述第1實施形態之玻璃層11之 KCVPaC^TeCM^O3所構成的不含Pb的v系低融點玻璃。 又，作為參考例2，使用構成上述第1實施形態之電子零件 收納構材30的八12〇3。 然後’藉由改變實施例1〜5、比較例1、參考例1及2之 各構材的溫度，測定各構材的伸長率。又，所謂伸長率，係 指將任意溫度下之構材之伸長量（由任意溫度下之長度減去 室酿(30 C)時之基準長度的量），除以室溫時之基準長度的 值。然後，求取連結了室溫下之伸長率與25〇〇c下之伸長率 的直線的斜率’作為301以上且250°C以下之溫度範圍中的 熱膨脹係數。 如圖8所示般，作為伸長率測定的實驗結果，係藉由於22 S 201238857 13 thickness t3 $ about 3.3μηι or more and about 12MJn or less, the thickness t3 of the oxide film layer 13 can be sufficiently ensured, so that the 2〇3 film constituting the oxide film layer U and the glass layer 11 can be formed. The V-based low melting point glass is very sticky. Further, in the first embodiment, as described above, the metal base material 12 is formed of a 42Ni_(2 to 6)Cr-Fe alloy, and the metal base material 12 can be formed on the entire surface of the metal base material 12. An oxide film layer 13 composed of a C]:2〇3 film. Further, it is possible to suppress a case where the thermal expansion coefficient α2 of the metal base material 12 due to the excessive Cr content is large, and the thermal expansion coefficient α2 of the metal base material 12 is significantly different from the thermal expansion coefficient αΐ of the glass layer n. Thereby, it is possible to suppress cracking or the like due to a difference in thermal expansion on the glass layer 11 or the metal substrate 12. Further, when the metal base material 12 contains 42% by mass of Ni, the thermal expansion coefficient α2 of the metal base material 12 can be made small. Thereby, the thermal expansion coefficient α2 of the metal base material 12 can be made closer to the thermal expansion coefficient α1 of the glass layer 11 composed of the low melting point glass of the metal material which is generally smaller than the thermal expansion coefficient. The bean fruit can be more inhibited from the cracking of the glass layer due to the difference in thermal expansion. Further, in the first embodiment, as described above, when the metal base material 12 is made of a 42Ni-(3~6)Cr-Fe alloy, the thermal expansion coefficient αΐ of the glass layer can be made metal. Since the thermal expansion coefficient α2 of the substrate 12 satisfies the relationship of -15 X10 7 ^ α2 - α 1 S 5 X10 7 , it is possible to surely suppress the occurrence of cracking of the glass layer 11 composed of the ν-based low-melting glass. Further, in the first embodiment, as described above, by forming the oxide film layer 100142851 23 201238857 13 so as to surround the entire surface of the two surfaces of the metal substrate, it is only in the metal substrate 12v. The oxide film layer 13 is prevented from being placed on the surface of the substrate. Further, unlike in the case of only the metal substrate 12: = the film layer 13, the shape = the portion of the oxidized substrate 12 into the (four) | m ^ 130 ^ need to be metal, and can accommodate (four) silk Film layer 13. In addition, since the oxide film layer 3 composed of the pure (10) is formed so as to surround the entire surface of the metal substrate 12, the metal substrate η can be lifted and the t# property can be improved. In the first embodiment, As described above, by the thermal expansion coefficient of the glass layer n in the temperature range of about 3 (rc or more and about 25 G ° C or less) and the thermal expansion of the electronic component storage member 3? When the coefficient α3 (about 65×10 7 /° C.) satisfies the relationship of ΐ$αΐ~α3 (=^ 5xl〇-7)g1〇xl〇-7, when the glass layer 11 is joined to the electronic component storage member 3〇 When the solidification temperature (about 300 ° C) is lowered, the stress generated in the glass layer 11 composed of the v-based low-melting glass can be reduced, so that the glass composed of the V-based low-melting glass can be suppressed. In the first embodiment, as described above, the thermal expansion coefficient α of the glass layer 11 is about 3 (about 70 x 10 7 ) in a temperature of about 3 (rca and about 250 ° C or less). /C) The thermal expansion coefficient α3 of the electronic component storage member 30 (about 65 >< 10 force. 〇 Satisfy 〇 Sal-~cx3 (= about 5 χ 10·7) $ ΐ〇χΐ〇 -7 And the thermal expansion coefficient αΐ of the glass layer 11 and the thermal expansion coefficient of the metal substrate 12 are 100142851 24 201238857 α2 (about 55xl (T7/°C or more and about 75xl (T7/°C or less) 4_15χ10-7$α2~ alShio. Even if the glass layer η is applied to both the electronic component storage structure and the electronic component storage member 3G, the tensile stress is applied to both the metal substrate 12 and the electronic component storage member 3G, and thus only the metal substrate 12 and One of the electronic component storage members is ruptured by applying the glass layer 11 to the glass layer 11. The 月 and the moon opening V are different and can be suppressed. In the embodiment, as described above, by the metal substrate 12 At about 4 points, it is about 30C, which is less than the partial pressure of gasification of f and Nl, and is greater than the temperature of the humidified helium gas that can oxidize Cr, and the temperature under (C) Ca. In the above-mentioned preferred oxidation, it is easy to ensure that the thickness of the film layer 13 is more surely ensured only on the surface of the (4) MM-treated metal substrate 12. The scale formed by the skin mold (Example) Next, Referring to Figure 2 and Figure 7 to Figure 17, the brother and the moon in order to confirm the effect of the first implementation of the sadness In the measurement of the thermal conductivity of the lamp, and the measurement of the coefficient of thermal expansion, the thermal expansion coefficient described below is determined as the metal substrate 12 of the first embodiment described above, as shown in the figure σ. Example %~5 of % ^, in the Fe-based alloy containing Fe and Fe, there is Μϋ. - 100142851 25 201238857 Specifically, as Example 1, the use contains 2 mass ° / Fe alloy of 〇Cr (42Ni-2Cr-Fe alloy). Further, as Example 2, a Fe-based alloy (42Ni-3Cr-Fe alloy) containing 3% by mass of 0 was used, and as Example 3, a Fe-based alloy containing 4% by mass of 0 (42Ni-4Cr-Fe alloy) was used. ). Further, as the fourth embodiment, a Fe-based alloy (42Ni-5Cr-Fe alloy) containing five masses of Dong% Cr was used. Further, as Example 5, a Fe-based alloy (42Ni-6Cr-Fe alloy) containing 6 mass% of Cr was used. On the other hand, as Comparative Example 1 with respect to Examples 1 to 5, 42 mass was used. / Fe and Ni, and Fe-free alloy (42Ni-Fe alloy). In addition, as a reference example 1 of the metal substrate of the first embodiment, a p-based v-based low-melting point glass composed of KCVPaC^TeCM^O3 constituting the glass layer 11 of the first embodiment is used. Further, as a reference example 2, eight 12 〇 3 constituting the electronic component housing member 30 of the above-described first embodiment is used. Then, the elongation of each member was measured by changing the temperatures of the members of Examples 1 to 5, Comparative Example 1, and Reference Examples 1 and 2. In addition, the elongation means the amount of elongation of the member at any temperature (the amount of the reference length when the temperature is reduced from the temperature at any temperature (30 C)), and the reference length is divided by the room temperature. value. Then, the slope ' of the straight line connecting the elongation at room temperature and the elongation at 25 〇〇c was determined as the coefficient of thermal expansion in a temperature range of 301 or more and 250 °C or less. As shown in Fig. 8, as an experimental result of the elongation measurement, it is due to

100142851 26 S 201238857 42Ni-Fe合金（比較例1 係數}。又，藉由增大Cr二?’而可增大伸長率(熱膨脹 ，、/曰八U添加1，可增加伸長率。 另卜；系低融點玻璃之破璃轉移點μ Μ 度範圍，比較例k42Ni_p a轉移』(285 C)為止的溫 ^ ^ e 口金的伸長率變得相當小於v 糸低融點㈣（參考例 42Ni-沿-Fe合金之伸 長'又’貫她例1之 1)之伸長率。另一 ,、;v系低融點玻璃（參考例 一方面，實施例2〜5之421sn η ΜΓν p入 金的伸長率係近似 之儀-(3〜6)Cr-Fe合 值。 純融點_(參相1)之伸長率的 另外，如圖7及同0 _ 以上且25(TC以下：，般’作為熱膨服係數，係於3〇°C 1)之熱膨脹係數α1 A又觀圍。中’ V系低融點玻璃(參考例 係數α3為65x1〇-7/<t。/C ’ Al2〇3(參考例2)之熱膨脹 例1)之熱膨脹係數/、σ果判明V系低融點玻璃（參考 滿足Mali卜二^2〇3 (參考例2)之熱膨脹係數(Χ3 〇 )各1〇χ1 (Γ7的關传。 另外，於30¾以上 關係 之42Ni-Fe合金沾也5〇 C以下之溫度範圍中’比較例j 於以低_麵(、3鱗a2為_讀，判明相較 而僅小32_竹。_；例”之熱膨脹係數叫72咖％ 亦印’在將由42Ni-Fe合金所構成之fcf_ 較例1之金屬基材邀v么 舟乂疋比 ” v系低融點玻璃依密封溫度（約37〇。匚 以上且约備。C以下）進行接合時，由於熱膨脹係數之差⑽ -al)較大(-32><1〇-7/。「、 故認為於冷卻時在由.V系低融點 100142851 € 27 201238857 玻璃所構成之玻璃層容易發生破裂（裂痕）。 另外，於3〇C以上且250。(：以下之溫度範圍中，實施例1 全之膨脹係數α2為56 X10_7/。〇，判明相 較v系低融點玻瑪（參考例1)之熱膨脹係數 α1(72χ1〇·7/°〇 僅小16Xl〇 /(：。亦即，在將由42Ni-2Cr-Fe合金所構成之 貝她例1之金屬基材與v系低融點玻璃依密封溫度進行接 合時"’由於熱膨脹係數之差大至某程度㈠6χΐ〇-7/ΐ)，故認 為冷部時在由V系低融點玻璃所.構成之玻璃層有發生破裂 的可能性。 另方面’於3〇ΐ以上且25〇ΐ以下之溫度範圍中，實施 例7。之42Nl_(3〜6)Cr-Fe合金的熱膨脹係數α2為 62x1(r7/°c以上且74xl(r7rc以下與ν系低融點玻璃（參考 例Ό之熱膨脹係數al(72xl〇-Vc)滿足-ΐ〇χ10、α2_ 化2咐7的_。亦即’在將由條-(3〜6)Cr-Fe合金所 構成之實施例2〜5之金屬基材與^低融點玻璃依密封溫 度進打接合時，由於錢有熱膨脹餘之差，故認為可抑制 冷部時在纟V綠雜朗所構权麵層射破裂的情 形。其結果，可認為適合使用撕(3〜咖如合金作為金 屬基材。 ^ (濕潤性測定） 以下說明之制性測定中，作為對應上述第i實施料之 金屬基材12的實施例6〜9係、使用·MCr.Fe合金，作為 100142851 28 201238857 實施例10〜13係使用42Ni-6Cr-Fe合金。又，於實施例6 9 中，使進行Cr優先氧化時之溫度條件分別相異，且 々、X施 例10〜13中，使進行Cr優先氧化時之溫度條件分別相異。 又，Cr之優先氧化係於露點為如^之濕潤氫氣環境中進行 30分鐘。 具體而g，如圖10及圖11所示般，作為實施例6及 係於900Ϊ之溫度條件下進行Cr優先氧化。又，作為實施 例7及11’係於l〇〇(TC之溫度條件下進行&優先氧化。又， 作為實施例8及12,係於1100。(：之溫度條件下進行Cr優先 氧化。又，作為實施例9及13，係於il5(TC之溫度條件 進行Cr優先氧化。 、 然後，測定實施例6〜13之於42Ni-4(6)Cr-Fe合金表面上 所升y成之由Cr2〇3所構成的氧化皮膜層的厚度t3(參照圖2)。 另外’如圖12所示，在實施例6、8〜1〇、12及13之由金 屬基材112與氧化皮膜層113所構成的蓋HO表面上塗佈ζ 系低融點坡續之糊料114。同樣地，在由从 所構成之蓋主二，、 ） 表面上塗佈V系低融點玻璃之糊料μ 時，在蓋11〇 此 表面上之3處，分別塗佈寬度w相異 114。具體而一 n '、 言，在蓋HO表面上塗佈寬度W1為290μιη的 糊料114a、實谇 見度W2為4〇〇μιη之糊料114b、與寬度W3為 460μιη的糊粗^ 寸U4c。此時，糊料114a、114b及114c之厚戶 t4均塗佈成8〇μιηβ 又100142851 26 S 201238857 42Ni-Fe alloy (Comparative Example 1 coefficient}. Further, the elongation can be increased by increasing Cr?? (thermal expansion, / / 8 U added 1 can increase the elongation. The range of the μ Μ degree of the glass transition point of the low melting point glass, the elongation of the temperature ^ ^ e gold of the comparative example k42Ni_p a 』 (285 C) becomes considerably smaller than v 糸 low melting point (4) (Reference Example 42Ni- The elongation along the -Fe alloy 'is further than the elongation of Example 1). Another, v; low melting glass (refer to the example, on the one hand, the 421sn η ΜΓ ν p of the embodiment 2~5 into the gold elongation The rate is approximating - (3~6) Cr-Fe value. The elongation of pure melting point _ (phase 1) is also shown in Figure 7 and the same as 0 _ and 25 (TC below: The thermal expansion coefficient is based on the thermal expansion coefficient α1 A of 3〇°C 1). The middle 'V-low melting point glass (reference example coefficient α3 is 65x1〇-7/<t./C 'Al2〇) 3 (Reference Example 2) The thermal expansion coefficient of the thermal expansion example 1), σ, and the V-based low-melting point glass (refer to the thermal expansion coefficient (Χ3 〇) of the Mali Bu 2^2〇3 (Reference Example 2) Χ1 (Γ7's pass. Another In the temperature range of 〇 以下 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 The thermal expansion coefficient of the example is called 72%%. It is also printed in the fcf_ which is composed of 42Ni-Fe alloy. Compared with the metal substrate of the first example, the v-based low-melting glass is sealed at a temperature of about 37 〇.匚 且 且 。 。 。 。 。 。 。 。 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C Melting point 100142851 € 27 201238857 The glass layer formed by glass is prone to cracking (cracking). In addition, in the temperature range below, the expansion coefficient α2 of Example 1 is 56 X10_7/. 〇, it is found that the coefficient of thermal expansion α1 (72χ1〇·7/°〇 is only 16Xl〇/(:., that is, it will be composed of 42Ni-2Cr-Fe alloy) compared to the v-low melting point of the V-line (Reference Example 1). When the metal substrate of Example 1 and the v-type low melting point glass are joined at the sealing temperature, the difference between the thermal expansion coefficients is large to some extent (1) 6χΐ -7/ΐ), it is considered that there is a possibility of cracking in the glass layer composed of V-based low-melting glass in the cold part. In other respects, in the temperature range of 3〇ΐ or more and 25〇ΐ or less, Example 7. The coefficient of thermal expansion α2 of the 42Nl_(3~6)Cr-Fe alloy is 62x1 (r7/°c or more and 74xl (lower melting point glass below r7rc and ν system (refer to the thermal expansion coefficient of the reference example a(72xl〇) -Vc) _ _ 10, α 2 _ 2 咐 7 _. That is, when the metal substrate of Examples 2 to 5 composed of the strip-(3 to 6) Cr-Fe alloy is bonded to the low-melting point glass according to the sealing temperature, since the money has a difference in thermal expansion, Therefore, it is considered that it is possible to suppress the occurrence of cracking in the structuring surface of the 纟V green hybrid when the cold part is formed. As a result, it is considered that it is suitable to use a tear (3 to a coffee such as an alloy as a metal substrate.) (Measurement of wettability) In the measurement of the properties described below, Example 6 to the metal substrate 12 corresponding to the above-described i-th embodiment 9 series, using MCr.Fe alloy, as 100142851 28 201238857 Examples 10 to 13 used 42Ni-6Cr-Fe alloy. Further, in Example 619, the temperature conditions for preferential oxidation of Cr were different, Further, in the X and X examples 10 to 13, the temperature conditions at which Cr is preferentially oxidized are different. Further, the preferential oxidation of Cr is carried out for 30 minutes in a humid hydrogen atmosphere having a dew point of, for example, g. As shown in Fig. 10 and Fig. 11, Cr was preferentially oxidized as Example 6 and at a temperature of 900 Torr. Further, as Examples 7 and 11', it was carried out under the temperature condition of TC. Further, as Examples 8 and 12, Cr was preferentially oxidized under the temperature conditions of 1100. Further, as Examples 9 and 13, il5 was preferentially oxidized under temperature conditions of TC. , measuring the surface of 42Ni-4(6)Cr-Fe alloy of Examples 6 to 13 The thickness t3 of the oxide film layer composed of Cr2〇3 is increased (see Fig. 2). Further, as shown in Fig. 12, the metal substrates of Examples 6, 8 to 1 , 12 and 13 are used. 112 and a surface of the cover HO formed of the oxide film layer 113 are coated with a paste 114 having a low melting point. Similarly, a V-based low melting is applied on the surface of the cover main body 2, When the glass paste μ is applied, the width w is different from each other at three places on the surface of the lid 11 . Specifically, a coating is applied on the surface of the lid HO with a width W1 of 290 μm. 114a, the solid visibility W2 is 4〇〇μιη paste 114b, and the width W3 is 460μιη thick paste U4c. At this time, the thick portions of the pastes 114a, 114b and 114c t4 are coated into 8〇μιηβ also

S 100142851 29 201238857 然後’藉由於410°C之溫度條件下進行燒成 ，去除糊料 114a、114b及114c内的黏結劑。藉此，如圖1S所示，糊料 114a、114b及114c(參照圖12)分別成為玻璃層llla、1Ub 及111c。其後，分別測定玻璃層iiia之寬度wia及厚度 t4a、玻璃層111b之寬度W2a及厚度t4b、玻璃層111c之寬 度W3a及厚度t4c。然後，分別求取玻璃層llla(lllb及llic) 之寬度及厚度相對於糊料114a(114b及114c)之寬度及厚度 的變化率。此時，在玻璃層111之寬度(厚度）大於糊料114 之寬度(厚度）的情況，將變化率設為正值，在玻璃層111之 寬度(厚度）小於糊料114之寬度(厚度）的情況，將變化率設 為負值。 如圖10所示般，在42Ni-4Cr-Fe合金中，實施例6(900°c) 中之氧化皮膜層的厚度t3為未滿Ο.ίμηι。亦即，可認為在 實施例6(900°C)中氧化皮膜並未形成充分厚度。另一方面’ 實施例7~9中（1000°C、1100°c、1150。〇中，氧化皮膜層之 厚度t3為0.3μπι以上。又，如圖11所示，在42Ni-6Cr-Fe 合金中，實施例 10〜13(900¾、i〇〇〇°C、1100°C、115〇°C) 之任一者中，氧化皮膜層之厚度t3均為〇.3μιη以上。 另外，溫度條件為9〇(TC之實施例6(4Cr)及實施例 10(6Cr)、溫度條件為l〇〇(TC之實施例7(4Cr)及實施例 ll(6Cr)、溫度條件110〇t：之實施例8(4Cr)及實施例 12(6Cr)、與溫度條件115〇°c之實施例9(4Cr)及實施例S 100142851 29 201238857 Then, the binder in the pastes 114a, 114b and 114c is removed by firing at a temperature of 410 °C. Thereby, as shown in Fig. 1S, the pastes 114a, 114b, and 114c (see Fig. 12) become the glass layers 111a, 1Ub, and 111c, respectively. Thereafter, the width wia and the thickness t4a of the glass layer iiia, the width W2a and the thickness t4b of the glass layer 111b, the width W3a of the glass layer 111c, and the thickness t4c were measured. Then, the rate of change of the width and thickness of the glass layers 111a and 11ll with respect to the width and thickness of the pastes 114a (114b and 114c) were respectively determined. At this time, in the case where 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 the width (thickness) of the glass layer 111 is smaller than the width (thickness) of the paste 114. In the case of the rate of change, 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 ί.ίμηι. That is, it is considered that the oxide film did not form a sufficient thickness in Example 6 (900 ° C). On the other hand, in Examples 7 to 9 (1000 ° C, 1100 ° C, 1150. In the crucible, the thickness t3 of the oxide film layer was 0.3 μm or more. Further, as shown in Fig. 11, in the 42Ni-6Cr-Fe alloy In any of the examples 10 to 13 (9003⁄4, i〇〇〇°C, 1100° C., 115° C), the thickness t3 of the oxide film layer is 〇.3 μmη or more. 9〇 (Example 6 (4Cr) of TC and Example 10 (6Cr), temperature condition l〇〇 (Example 7 (4Cr) of TC and Example ll (6Cr), temperature condition 110〇t: implementation Example 8 (4Cr) and Example 12 (6Cr), and Example 9 (4Cr) with temperature conditions of 115 ° C and examples

30 100142851 S 201238857 13(6Cr)的任一者中，使用有42Ni_6Cr_Fe合金之實施例 10〜13的氧化皮膜層的厚度t3，均分別大於使用有 42Ni-4Cr-Fe合金之實施例6〜9的氧化皮膜層的厚度t3。藉 此，判明在溫度條件為相同的情況，藉由增大Cr含量，可 增加乳化皮膜層之厚度t3。 另外’如圖14及圖16所示般，判明實施例6及1 〇(90〇°c) 中之寬度的變化率，均於所有的玻璃層111a、llib及lllc 中變小_4〇%。又，如圖15及圖Π所示般，實施例6及10 中之厚度的變化率，係除了實施例6之玻璃層Ula厚度(·2%) 以外為〇%以。甘 /、可s忍為因實施例6及1 〇中，氧化皮膜層 未充为或未完全形成，故呈濕雜低、V系低 化皮膜層未充分衆 之玻璃層⑴二狀態。因此’可認為朝寬度方向擴展 θ 之才多部分朝厚度方向***。 另方面，如圖14及圖16所示般，訾 12(1靴）、實施例9及13(叫）、與_^例8及 以上。又 例9及 寬度的變化率，係於所有玻璃層Iiia、nib^ 2⑽03)中 :如圖15及圖17所示般，實施例8及:為’°/° 声⑴ 參考例2中之厚度的變化率，传:實施 /叫及llle中減小德。其結果，，所有_ 12與貫施例9及13中 /、 在實施例8及 其濕潤性高，I v ^於氧化皮膜層充分形成，故Μ為 狀態。藉此，可認& ^點破璃與氧化皮_充分密 I為其抑制朝寬度方向擴展：黏的 100142851 吸嘴層111之30 100142851 S 201238857 13 (6Cr), the thickness t3 of the oxide film layers of Examples 10 to 13 using the 42Ni_6Cr_Fe alloy is larger than those of Examples 6 to 9 using 42Ni-4Cr-Fe alloy, respectively. The thickness of the oxide film layer is t3. Therefore, it was found that the thickness t3 of the emulsified film layer can be increased by increasing the Cr content in the case where the temperature conditions are the same. Further, as shown in Fig. 14 and Fig. 16, it was found that the rate of change in the width in the examples 6 and 1 〇 (90 〇 ° c) was smaller in all the glass layers 111a, llib, and lllc _4%. . Further, as shown in Fig. 15 and Fig. 5, the rate of change of the thickness in Examples 6 and 10 was 〇% in addition to the thickness (·2%) of the glass layer Ula of Example 6. Since the oxide film layer was not filled or not completely formed in Examples 6 and 1 , the wet film was low, and the V-based film layer was not sufficiently in the state of the glass layer (1). Therefore, it can be considered that only a part of the θ extending in the width direction is swelled in the thickness direction. On the other hand, as shown in Figs. 14 and 16, 訾 12 (1 boot), Examples 9 and 13 (call), and _^ 8 and above. Further, the change rate of the example 9 and the width is in all the glass layers Iiia and nib^2(10)03): as shown in Figs. 15 and 17, the embodiment 8 and the following are: '°/° sound (1) thickness in the reference example 2 The rate of change, pass: implementation / call and llle reduce the German. As a result, all of the _ 12 and the examples 9 and 13 were in the case of Example 8 and the wettability was high, and I v ^ was sufficiently formed in the oxide film layer, so that the state was in the state. By this, it is possible to recognize & ^ point of the glass and scale _ fully dense I for its inhibition to expand in the width direction: sticky 100142851 nozzle layer 111

31 S 201238857 部分朝厚度方向移動，而不朝厚度方向***，於黏結劑之體 積份、寬度方向及厚度方向上變小。 亦即，判明於_叱以上之溫度範圍中進行〇優先氧化 者’由於可作錢V約㈣點麵與氧化纽層充分密黏 的狀態，故較佳。另一方面，在大於H5(rc之溫度範圍中 進行Cr優先氧化者，因需要高耐熱性的設備，故可認為較 佳係依1000 C以上且1150。(：以下之溫度範圍進行Cr優先氧 化0 另外，相較於實施例8及12(11〇〇。〇，由於實施例9及 13(1150°C)的寬度變化率及厚度變化率的減少幅度整體性 地較少’故可認為更佳係於115〇。(：之溫度條件下進行Cr優 先氧化。 (第2實施形態） 接著，參照圖18，說明本發明之第2實施形態。此第2 實施形態之氣密密封用蓋材201，係針對與上述第1實施形 態相異、金屬基材212為由3層之包層材所構成的情況進行 說明。 本發明第2實施形態之氣密密封用蓋材201中蓋210的金 屬基材212，係如圖18所示般，藉由使配置於玻璃層11側 (Z1側）的第1層212a、配置於第1層212a之Z2側（玻璃層 11的相反侧）的第2層212b、與配置於第2層212b之Z2側 (玻璃層11的相反側）的第3層212c接合而形成，即由所謂 100142851 32 201238857 的3層之包層材所構成。又，第j層212&與第3層212c均 為由含有約42質量％之所、約6 f量％之&、與Fe的一 般Fe系合金(樣卜6Cr-Fe合金)所構成。又，第2層以沘 係由含有約42質量％之沁、與Fe的一般Fe系合金(42Ni_Fe 合金)所構成。 另外’構成第1層212a及第3層212c的42Ni 6Cr_Fe合 金的熱膨脹係數oc4係構成為約75χ1〇_7/<3〇。又，構成第2 層212b之42Ni-Fe合金的熱膨脹係數α5構成為約 40x10 /c。亦即，構成為第！層212a及第3層212c之熱 膨脹係數α4(約75Xl(rVt)，係大於玻璃層u之熱膨脹係 數ctl(約7〇xl07/C) ’且第2層212b之熱膨脹係數ct5(約 4〇xl(T7/°C)係小於玻璃層U的熱膨脹係數α1。 於此，第2實施形態中，合計第丄層212a、第2層212b 及第3層212c的厚度（蓋210的厚度)tl，為約〇 lmm。又， 第1層212a及第3層212c係於z方向上具有相同厚度t5, 而第2層212b係於Z方向上具有厚度（6。於此，厚度t5 較佳為厚度t6的約50%以上。亦即，合計了第！層212a及 第3層212c之厚度(2xt5)較佳為蓋21〇之厚度tl(=2xt5+t6) 的約50%以上（約0.05mm以上）。其結果，於約3〇r以上且 約250 C以下之溫度範圍中，構成金屬基材212之包層材的 熱％脹係數α2為約55xl〇-7/°c以上且約75xi〇-7/〇c以下。亦 即，於約30°C以上且約25(TC以下之溫度範圍中，構成玻璃 100142851 „ 201238857 層11之V系低融點玻璃的熱膨脹係數α1(約7〇><1〇力。〇、 與構成金屬基材212之包層材的熱膨脹係數α2係滿足 _15χ10·7$(χ2-α1$5χ1(Τ7 的關係。 另外，第1層212a之Ζ1侧的面及側面上，形成有主要由 &2〇3所構成的氧化皮膜層213a，且於第3層212c之22侧 的面及側面，形成有主要由C]：2〇3所構成的氧化皮膜層 213b。此氧化皮膜層213a及213b，係分別使第1層212& 及第3層212c的42Ni-6Cr-Fe合金中所含有的Cr於第工層 212a之Z1側的面及側面、以及第3層212c之以側的面及 側面進行氧化所形成。又，關於第2實施形態的其他構成， 係與上述第1實施形態相同。 接著，參照圖18，說明本發明第2實施形態之氣密密封 用蓋材201的製造製程。 首先，準備具有既定厚度之由42Ni-Fe合金所構成的板材 (未圖示）。又，準備由42Ni-6Cr-Fe合金所構成、且具有由 42Ni-Fe合金所構成之板材之厚度的約5〇%以上之厚度的2 片板材。然後’依以由42Ni-6Cr-Fe合金所構成之板材挾持 由42Ni-Fe合金所構成之板材的狀態，在對由42Ni_Fe合金 所構成之板材與由42Ni-6Cr-Fe合金所構成之板材的一對板 材施加有既定壓力的狀態下進行接合。藉此，如圖18所示， 形成使由42Ni-6Cr-Fe合金所構成之第1層212a、由42Ni-Fe 合金所構成之第2層212b、與由42Ni_6Cr-Fe合金所構成之 100142851 34 201238857 第3層212c依序積層的狀態下所接合的3層之包層材。此 時，第1層212a及第3層212c之厚度t5均為第2層21沘 之厚度t6的約5〇%以上。其後，藉由將包層材切斷為既定 形狀，形成金屬基材211。 其後，藉由依與上述第1實施形態相同的條件進行&優 先氧化，而在第1層212a之Z1側的面及侧面，形成主要由 Cr2〇3所構成的氧化皮膜層213a，且於第3層212c之Z2側 的面及側面，形成主要由Cr*2〇3所構成的氧化皮膜層213b。 又，本發明第2實施形態之其他製造製程係與第丨實施形態 相同。 第2實施形態中，如上述般，由於氣密密封用蓋材2〇1 具備有形成於金屬基材212表面上之主要由cr2〇3皮膜所構 成的氧化皮膜層213a及213b、與形成於氧化皮膜層213a 表面上之由不含Pb之V系低融點玻璃所構成的玻璃層u， 故可使金屬基材212與電子零件收納構材3〇(參照圖4)充分 接合。又’由於氣密密封用蓋材201具備含有42Ni_6Cr_Fe 合金的金屬基材212,故相較於在基材中使用陶瓷材料的情 況’可減小氣密密封用蓋材201的厚度tl。又，藉由使金屬 基材212含有42Ni-6Cr-Fe合金，則可於金屬基材212表面 上輕易形成由〇2〇3皮膜所構成的氧化皮膜層213&及213卜 另外，第2實施形態中，如上述般，由於使金屬基材 構成為藉由使第1層212a、配置於第1層2l2a之Z2側的 100142851 35 201238857 第2層212b、與配置於第2層212b之Z2側的第3層212c 接合而形成的3層包層材所構成，且使第1層212a與第3 層212c為由42Ni-6Cr-Fe合金所構成，使第2層212b為由 42Ni-Fe合金所構成，故相較於金屬基材212為僅由1層所 構成的情況’藉由將熱膨脹係數不同之異種金屬材料彼此接 合，則可輕易地調整金屬基材212的熱膨脹係數α2。又， 由於可在氣密密封用蓋材201兩表面上配置由42Ni-6Cr-Fe 合金所構成的第1層212a及第3層212c，故可於金屬基材 212之兩表面（第1層212a之Z1側的面及第3層212c之Z2 側的面）上为別形成由Ci*2〇3皮膜所構成的氧化皮膜層213 a 及213b。藉此，與在金屬基材212之兩表面的僅其中一面 上形成有乳化皮膜層的情況不同’可防止將玻璃層11錯言吳 形成於未形成有氧化皮膜層之金屬基材212表面上的情形。 另外，第2實施形態中，如上述般，藉由使金屬基材212 之第1層212a、第2層212b及第3層212c為由含有42質 量％之Ni的Fe系合金所構成，則可使第1層2l2a、第2 層212b及第3層212c的熱膨脹係數均減小。藉此，可使金 屬基材212之熱膨脹係數α2確實接近由熱膨脹係數一般小 於金屬材料之V系低融點玻璃所構成之玻璃層^的熱膨脹 係數αΐ。又，若使第1層212a及第3層212c為由一般之 42Ni-6Cr-Fe合金所構成，並使第2層212b為由一般之 42Ni-Fe合金所構成，則可形成容易取得的Fe系合金，在 100142851 36 201238857 對應至玻璃層11所形成之區域的金屬基材212表面上开;{成 由〇2〇3皮膜所構成的氧化皮膜層213a及213b，並使金屬 基材212之熱膨脹係數α2接近由v系低融點玻璃所構成之 玻璃層11的熱膨脹係數(xl。 另外’第2實施形態中，如上述般’藉由使第1層 及第3層212c的熱膨脹係數α4(約75><10力。〇大於玻壤居 11之熱膨服係數αΐ (約7〇xl〇_7/°c)，並使第2層2121>之拥 膨脹係數α5(約4〇xlO_7/°C)小於玻璃層丨丨之熱膨服係數 cxl，則可調整第1層212a之厚度t5、第2層212b之厚尹 t6及第3層212C之厚度t5，藉此使金屬基材212整體的熱 膨脹係數α2接近玻璃層11的熱膨脹係數α1。 另外’第2實施形態中’如上述般，藉由使合計第1居 212a及第3層212c的厚度（2xt5)，為蓋21〇之厚度 tl(=2xt5+t6)之約50%以上’則可使玻璃層丨丨之熱膨脹係數 αΐ與金屬基材212之熱膨脹係數α2確實滿s_15xl〇-7^a2 -α1$5χ10·7的關係，故可確實抑制在由V系低融點玻璃所 構成之玻璃層11所發生的破裂（裂痕）。又，第2實施形態 之其他效果係與上述第1實施形態相同。 (實施例） 接著’參照圖18〜圖21 ’說明為了確認第2實施形態之效 果而進行的熱膨脹係數測定。 (熱膨脹係數測定） 100142851 37 201238857 以下說明之熱膨脹係數測定，係如圖19所示般，作為搿 應上述第2實施形態之金屬基材212的實施例14〜18，係構 成為使用具有由42Ni-6Cr-Fe合金所構成之第1層21以、由 42Ni-Fe合金所構成之第2層212b、與由42Ni-6Cr-Fe合金 所構成之第3層212c的3層包層材，且第1層212a之厚户 與第3層212c之厚度的合計(2xt5(參照圖18))相對於蓋210 之厚度tl的比率（板厚比率）相異。 具體而言’作為實施例Μ，將第1層212a及第3層212c 之厚度合計(2xt5)設為蓋210之厚度tl的12.5%，並將第2 層212b之厚度t6(參照圖18)設為蓋210之厚度tl的87 5%。 又，作為實施例15，將厚度合計(2xt5)設為厚度tl的25%， 並將厚度t6設為厚度tl的75%。又，作為實施例16，將厚 度合計(2xt5)設為厚度tl的50%，並將厚度t6設為厚度tl 的50%。又，作為實施例17’將厚度合計(2xt5)設為厚度^ 的67%，並將厚度t6設為厚度tl的33%。又，作為實施例 W ’將厚度合計(2xt5)設為厚度tl的75%，並將厚度t6設 為厚度tl的25%。 另外’作為相對於實施例14〜18的比較例1，使用與上述 第1實施形態之比較例1相同之由42Ni-Fe合金所構成的金 屬基材。亦即，作為比較例1，使用42Ni-6Cr-Fe合金之厚 度t5之板厚比率為〇%的金屬基材。又，作為比較例3，使 用與上述第1實施形態之實施例5相同之由42Ni-6Cr-Fe合 100142851 38 201238857 金所構成的金屬基材。亦即’作為tt較例3，使用侧.Fe 合金之厚度t5之板厚比率為的金屬基材。又與第i 實施形態同樣地’使用V系低融點玻璃作為參考例】，並使 用Al2〇3作為參考例2。 然後，依與上述第1實施形態之熱膨脹係數測定相同的方 法，求取實施例14〜18、比較例1及3、參考例i及2之各 構材的伸長率與於3(TC以上且25(rc以下之溫度範圍中的 熱膨脹係數。 如圖20所示般，作為伸長率測定的實驗結果，係藉由增 加42Ni-6Cr-Fe合金的板厚比率’而可增加伸長率（熱膨脹係 數）。 另外，於V系低融點玻璃之玻璃轉移點（285。〇為止的溫 度範圍，實施例14(12.5%)及實施例15(25%)之伸長率係小 於V系低融點玻璃（參考例1)的伸長率。另一方面，實施例 16〜18及比較例3(50%〜1〇〇%)的伸長率係近似V系低融點 玻璃（參考例1)之伸長率的值。 另外，如圖19及圖21所示般，判明作為熱膨脹係數，係 於30°C以上且250°C以下之溫度範圍中，實施例14(12.5%) 之熱膨脹係數α2為45χ1〇·7Λ：，相較V系低融點玻璃（參考 例1)之熱膨脹係數α1(72χ10·7Λ：)僅小27><10力。(：。又，實 施例15(25%)之熱膨脹係數α2為51xl(T7/°C，相較V系低 融點玻璃（參考例1)之熱膨脹係數al(72xl(T7/°c)僅小 100142851 39 201238857 21X10 7/°C。亦即，在將實施例14(12.5%)及實施例15(25%) 之金屬基材、與V系低融點玻璃依密封溫度（約370°C以上 且約4〇〇C以下）進行接合時，由於熱膨脹係數之差（α2 —αΐ) 較大（27(21 )χ ΐ〇 7/。〇，故認為於冷卻時在由ν系低融點玻 璃所構成之玻璃層容易發生破裂（裂痕）。 另一方面，於3〇。(：以上且250°C以下之溫度範圍中，實施 例16〜18及比較例3(5〇%〜1〇〇%)之熱膨脹係數α2為 58x10 /◦以上且74><1〇-7/。〇以下，判明其與ν系低融點玻 璃（參考例U之熱膨脹係數α1(72χ1(Γ7η：)滿足-Ι4χ10_7$α2 — α1$ 2x10-7的關係。亦即，在將實施例16〜18之金屬基材 與V系低融點玻璃依密封溫度進行接合時，由於不致有熱 脑/服係數之差’故認為可抑制冷卻時在由V系低融點玻璃 所構成之玻璃層發生破裂的情形。其結果，可認為適合以將 42Ni-6Cr-Fe合金之板厚比率設為金屬基材（蓋）之5〇%以上 者作為金屬基材。 尚且，此次揭示之實施形態及實施例，應認為其所有要點 僅為例示、而非限制。本發明範圍並非上述實施形態及實施 例之說明内容’而為由中請專利範圍所揭示，進而包括與申 請專利範圍同等之意義及範圍内的所有變更。 例如，上述第1實施形態中，表示金屬基材12為由 42Ni-(2〜6)Cr-Fe合金所構成的例，且於上述第2實施形態 中，表不金屬基材212為由使由42Ni-6Cr-Fe合金所構成之 100142851 40 201238857 第1層212a、由42Ni-Fe合金所構成之第2層212b、由 42Ni-6Cr-Fe合金所構成之第3層212c接合的包層材所構成 的例，但本發明並不限定於此。本發明中，構成金屬基材之 金屬材料並不需要含有Ni，若含有Cr即可。 另外’上述第1及第2實施形態中，雖表示在配置坡嘴展 11之部分以外亦形成有主要由CoO3皮膜所構成之氧化皮 膜層13(213a及213b)的例，但本發明並不限定於此。本發 明中，亦可僅在配置玻璃層的部分形成氧化皮膜層。 另外，上述第2實施形態中，雖表示金屬基材212為由使 第1層212a、第2層212b及第3層212c接合的3層包層 材所構成的例，但本發明並不限定於此。例如，亦可構成為 使由42Ni-6Cr-Fe合金所構成之第1層與由42Ni-Fe合金所 構成之第2層接合的2層包層材所構成。又，亦可構成為由 接合有4層以上的包層材所構成。 另外，上述第2實施形態中，雖表示第1層212a與第3 層212c為由具有相同組成的42Ni-6Cr-Fe合金所構成的 例，但本發明並不限定於此。本發明中，第1層212a之級 成與第3層212c的組成亦可相異。此時，較佳係配置於破 璃層11側之第1層212a的Cr含有率為約3質量％以上。 另外，上述第1及第2實施形態中，雖表示玻璃層11為 由含有V2〇5_P2〇5-TeO-Fe203且不含Pb之V系低融點坡續 所構成的例，但本發明並不限定於此。本發明中，玻璃層亦 100142851 41 201238857 可為V系低融點玻璃以外之不含Pb的玻璃材料。此時，藉 由使用在約400°C以下之溫度條件下融解的玻璃材料，則可 減小密封時之熱對水晶振盪器的影響。 另外’上述弟1及第2實施形態中，雖表示將水晶振還号 20收納於電子零件收納用盒1〇〇中的例，但本發明並不限 定於此。例如，亦可將SAW濾波器（表面彈性波濾波器）收 納於電子零件收納用盒中。 【圖式簡單說明】 圖1為表示本發明第1實施形態之氣密密封用蓋材之構成 的立體圖。 圖2為沿著圖1之300-300線的剖面圖。 圖3為表示本發明第1實施形態之電子零件收納用盒之構 成的立體圖。 圖4為沿著圖3之400-400線的剖面圖。 圖5為用於說明本發明第1實施形態之氣密密封用蓋材之 製造製程的剖面圖。 圖6為用於說明本發明第1實施形態之電子零件收納用盒 之製造製程的剖面圖。 圖7為表示為了確認本發明第1實施形態之效果而進行之 熱膨脹係數測定之實驗結果的表。 圖8為表示為了確認本發明第1實施形態之效果而進行之 熱膨脹係數測定之實驗結果的圖表。 100142851 42 201238857 圖9為表示為了確認本發明第丨實施形態之效果而進行之 熱膨脹係數測定之實驗結果的圖表。 圖10為表不為了確認本發明第i實施形態之效果而進行 之氧化皮膜層厚度測定之實驗結果的表。 圖11為表示為了確認本發明第丨實施形態之效果而進行 之氧化皮膜層厚度測定之實驗結果的表。 圖12為表示為了確認本發明帛i實施形態之效果而進行 之濕/間性测定之實驗方法的剖面圖。 圖13為表示為了確認本發明第丨實施形態之效果而進行 之濕潤性測定之實驗方法的剖面圖。 圖14為表示為了確認本發明第丨實施形態之效果而進行 之濕潤性測定之實驗結果的圖表。 圖15為表示為了確認本發明第丨實施形態之效果而進行 之濕潤性測定之實驗結果的圖表。 圖16為表示為了確認本發明第丨實施形態之效果而進行 之濕潤性測定之實驗結果的圖表。 圖17為表示為了確認本發明第丨實施形態之效果而進行 之濕潤性測定之實驗結果的圖表。 圖丨8為表示本發明第2實施形態之氣密密封用蓋材之構 成的剖面圖。 圖為表示為了確認本發明第2實施形態之效果而進行 之熱膨脹係數測定之實驗結果的表。31 S 201238857 The part moves in the thickness direction without bulging in the thickness direction, and becomes smaller in the volume, width direction and thickness direction of the binder. In other words, it has been found that the oxidized preferential oxidation in the temperature range of _ 叱 or more is preferable because it can be sufficiently viscous with the oxidized nucleus. On the other hand, in the case where the Cr preferential oxidation is performed in a temperature range larger than H5 (rc), since a device having high heat resistance is required, it is considered to be preferably 1000 C or more and 1150. (: The following temperature range is subjected to Cr preferential oxidation. In addition, compared with Examples 8 and 12 (11 〇〇. 〇, since the width change rate and the thickness change rate of Examples 9 and 13 (1150 ° C) are less overall, it is considered to be more (2nd Embodiment) Next, a second embodiment of the present invention will be described with reference to Fig. 18. The cover sheet for hermetic sealing according to the second embodiment is described. 201 is a case where the metal base material 212 is composed of a three-layer clad material, which is different from the above-described first embodiment. The lid 210 of the hermetic sealing cover material 201 of the second embodiment of the present invention is described. As shown in FIG. 18, the metal base material 212 is disposed on the Z2 side (opposite side of the glass layer 11) of the first layer 212a by the first layer 212a disposed on the glass layer 11 side (Z1 side). The second layer 212b is connected to the third layer 212c disposed on the Z2 side (opposite side of the glass layer 11) of the second layer 212b. The combination is formed by a three-layer cladding material of 100142851 32 201238857. Further, the j-th layer 212& and the third layer 212c are both contained in an amount of about 42% by mass and about 6% by volume. And a general Fe-based alloy of Fe (like a 6Cr-Fe alloy). Further, the second layer is composed of a general Fe-based alloy (42Ni_Fe alloy) containing about 42% by mass of lanthanum and Fe. Further, the coefficient of thermal expansion oc4 of the 42Ni 6Cr_Fe alloy constituting the first layer 212a and the third layer 212c is approximately 75 χ 1 〇 _7 / < 3 〇. Further, the thermal expansion coefficient of the 42Ni-Fe alloy constituting the second layer 212b Α5 is composed of about 40×10 /c. That is, the thermal expansion coefficient α4 (about 75×1 (rVt) of the first layer 212a and the third layer 212c is larger than the thermal expansion coefficient ctl of the glass layer u (about 7〇xl07/C). 'The thermal expansion coefficient ct5 of the second layer 212b (about 4 〇 xl (T7 / ° C) is smaller than the thermal expansion coefficient α1 of the glass layer U. Here, in the second embodiment, the second layer 212a and the second layer 212b are totaled. And the thickness of the third layer 212c (thickness of the cover 210) t1 is about 〇lmm. Further, the first layer 212a and the third layer 212c have the same thickness t5 in the z direction, and the second layer 2 12b has a thickness in the Z direction (6. Here, the thickness t5 is preferably about 50% or more of the thickness t6. That is, the thickness of the second layer 212a and the third layer 212c (2xt5) is preferably a cover. The thickness of 21〇 is about 50% or more (about 0.05 mm or more) of the thickness tl (= 2xt5 + t6). As a result, in the temperature range of about 3 〇r or more and about 250 C or less, the thermal swell coefficient α2 of the clad material constituting the metal base material 212 is about 55 x 1 〇 -7 / ° c or more and about 75 xi 〇 -7 /〇c below. That is, the thermal expansion coefficient α1 of the V-based low-melting glass constituting the glass 100142851 „201238857 layer 11 in a temperature range of about 30 ° C or more and about 25 (TC or less) (about 7 〇 > < 1 〇 force. The coefficient of thermal expansion α2 of the cladding material constituting the metal base material 212 satisfies the relationship of _15χ10·7$(χ2-α1$5χ1 (Τ7). Further, the surface and the side surface of the first layer 212a are formed on the side of the first layer 212a. An oxide film layer 213a mainly composed of & 2〇3 is formed, and an oxide film layer 213b mainly composed of C]:2〇3 is formed on the surface and the side surface on the 22nd side of the third layer 212c. The film layers 213a and 213b are such that the Cr layer contained in the 42Ni-6Cr-Fe alloy of the first layer 212& and the third layer 212c is on the Z1 side surface and the side surface of the work layer 212a, and the third layer 212c. The other configuration of the second embodiment is the same as that of the above-described first embodiment. Next, a hermetic sealing cover according to a second embodiment of the present invention will be described with reference to FIG. First, a plate made of 42Ni-Fe alloy having a predetermined thickness is prepared (not shown). Further, two sheets each having a thickness of about 5% by weight or more of a thickness of a sheet material composed of a 42Ni-Fe alloy and having a thickness of about 50% or more of the thickness of the sheet material composed of the 42Ni-Fe alloy are prepared. Then, 'by 42Ni-6Cr-Fe The sheet material composed of the alloy is held in a state of a sheet material composed of a 42Ni-Fe alloy, and a predetermined pressure is applied to a pair of sheets of the sheet material composed of the 42Ni_Fe alloy and the sheet material composed of the 42Ni-6Cr-Fe alloy. Thereby, as shown in Fig. 18, a first layer 212a composed of a 42Ni-6Cr-Fe alloy, a second layer 212b composed of a 42Ni-Fe alloy, and a 42Ni_6Cr-Fe alloy are formed. 100142851 34 201238857 The third layer 212c is a three-layer clad material joined in a state of being sequentially laminated. At this time, the thickness t5 of the first layer 212a and the third layer 212c are both the thickness t6 of the second layer 21沘. After about 5% or more, the metal substrate 211 is formed by cutting the cladding material into a predetermined shape. Thereafter, the oxidation is performed preferentially under the same conditions as in the first embodiment. The surface and the side surface of the Z1 side of the first layer 212a form an oxide film layer 21 mainly composed of Cr2〇3. 3a, and an oxide film layer 213b mainly composed of Cr*2〇3 is formed on the surface and the side surface of the Z2 side of the third layer 212c. Further, another manufacturing process system and a third embodiment of the second embodiment of the present invention In the second embodiment, the hermetic sealing cover member 2〇1 is provided with the oxide film layers 213a and 213b mainly composed of the Cr2〇3 film formed on the surface of the metal substrate 212, and The glass layer u composed of the V-based low-melting glass containing no Pb formed on the surface of the oxide film layer 213a allows the metal substrate 212 to be sufficiently bonded to the electronic component storage member 3 (see FIG. 4). Further, since the hermetic sealing cover member 201 is provided with the metal base material 212 containing the 42Ni_6Cr_Fe alloy, the thickness t1 of the hermetic sealing cover member 201 can be reduced as compared with the case where the ceramic material is used for the base material. Further, by including the 42Ni-6Cr-Fe alloy in the metal base material 212, the oxide film layers 213 & 213 and 213 which are formed of the 〇 2 〇 3 film can be easily formed on the surface of the metal base material 212. In the above-described configuration, the metal base material is configured such that the first layer 212a is placed on the Z2 side of the first layer 231a, and the second layer 212b is placed on the Z2 side of the second layer 212b. The third layer 212c is formed by joining three layers of cladding materials, and the first layer 212a and the third layer 212c are made of 42Ni-6Cr-Fe alloy, and the second layer 212b is made of 42Ni-Fe alloy. In the case where the metal base material 212 is composed of only one layer, the thermal expansion coefficient α2 of the metal base material 212 can be easily adjusted by joining different metal materials having different thermal expansion coefficients. Further, since the first layer 212a and the third layer 212c composed of the 42Ni-6Cr-Fe alloy can be disposed on both surfaces of the hermetic sealing cover member 201, the surface of the metal substrate 212 can be applied to the first layer (the first layer). The oxide film layers 213a and 213b composed of the Ci*2〇3 film are formed on the surface on the Z1 side of 212a and the surface on the Z2 side of the third layer 212c. Thereby, unlike the case where the emulsified film layer is formed on only one of the two surfaces of the metal substrate 212, the glass layer 11 can be prevented from being formed on the surface of the metal substrate 212 on which the oxide film layer is not formed. The situation. In the second embodiment, the first layer 212a, the second layer 212b, and the third layer 212c of the metal base material 212 are made of a Fe-based alloy containing 42% by mass of Ni. The thermal expansion coefficients of the first layer 2l2a, the second layer 212b, and the third layer 212c can be reduced. Thereby, the thermal expansion coefficient α2 of the metal base material 212 can be made close to the thermal expansion coefficient αΐ of the glass layer composed of the V-based low-melting glass having a thermal expansion coefficient generally smaller than that of the metal material. Further, when the first layer 212a and the third layer 212c are made of a general 42Ni-6Cr-Fe alloy, and the second layer 212b is made of a general 42Ni-Fe alloy, Fe can be easily formed. An alloy, which is opened on the surface of the metal substrate 212 corresponding to the region formed by the glass layer 11 at 100142851 36 201238857; {the oxide film layers 213a and 213b formed of the 〇2〇3 film, and the metal substrate 212 is The thermal expansion coefficient α2 is close to the thermal expansion coefficient (x1) of the glass layer 11 composed of the v-based low-melting glass. In the second embodiment, the thermal expansion coefficient α4 of the first and third layers 212c is obtained by the above. (about 75 >< 10 force. 〇 is greater than the thermal expansion coefficient α 玻 (about 7 〇 xl 〇 _7 / ° c) of the glass soil, and the second layer 2121 > the expansion coefficient α 5 (about 4 〇 xlO_7/°C) is smaller than the thermal expansion coefficient cxl of the glass layer, and the thickness t5 of the first layer 212a, the thickness of the second layer 212b, and the thickness t5 of the third layer 212C can be adjusted, thereby making the metal base The thermal expansion coefficient α2 of the entire material 212 is close to the thermal expansion coefficient α1 of the glass layer 11. Further, in the second embodiment, by the above, The thickness of the first layer 212a and the third layer 212c (2xt5) is about 50% or more of the thickness t1 (=2xt5+t6) of the lid 21〇, so that the thermal expansion coefficient αΐ of the glass layer and the metal substrate 212 can be Since the coefficient of thermal expansion α2 is completely equal to the relationship of s_15xl 〇-7^a2 - α1$5 χ 10·7, it is possible to surely suppress the crack (crack) occurring in the glass layer 11 composed of the V-based low-melting glass. The other effects of the embodiment are the same as those of the above-described first embodiment. (Examples) Next, the measurement of the thermal expansion coefficient in order to confirm the effect of the second embodiment will be described with reference to Fig. 18 to Fig. 21 (Measurement of thermal expansion coefficient) 100142851 37 201238857 The thermal expansion coefficient described below is as shown in Fig. 19, and Examples 14 to 18 which are the metal base material 212 of the second embodiment described above are configured to have a composition of 42Ni-6Cr-Fe alloy. The first layer 21 is composed of a second layer 212b made of a 42Ni-Fe alloy and a third layer of a third layer 212c made of a 42Ni-6Cr-Fe alloy, and the thick layer of the first layer 212a. The total thickness of the third layer 212c (2xt5 (refer to FIG. 18)) with respect to the thickness t of the cover 210 Specifically, the ratio of the thickness of the first layer 212a and the third layer 212c (2xt5) is set to 12.5% of the thickness t1 of the cover 210, and will be the same. The thickness t6 (see FIG. 18) of the second layer 212b is set to 87 5% of the thickness t1 of the cover 210. Further, as Example 15, the total thickness (2xt5) was set to 25% of the thickness t1, and the thickness t6 was set to 75% of the thickness t1. Further, as Example 16, the total thickness (2xt5) was set to 50% of the thickness t1, and the thickness t6 was set to 50% of the thickness t1. Further, as a total of 17', the total thickness (2xt5) was set to 67% of the thickness ^, and the thickness t6 was set to 33% of the thickness t1. Further, as a total example, the total thickness (2xt5) was set to 75% of the thickness t1, and the thickness t6 was set to 25% of the thickness t1. Further, as Comparative Example 1 with respect to Examples 14 to 18, a metal substrate composed of a 42Ni-Fe alloy similar to Comparative Example 1 of the above-described first embodiment was used. That is, as Comparative Example 1, a metal substrate having a thickness ratio t5 of 42Ni-6Cr-Fe alloy of 〇% was used. Further, as Comparative Example 3, a metal substrate composed of 42Ni-6Cr-Fe 100142851 38 201238857 gold similar to Example 5 of the first embodiment was used. That is, as a tt comparative example 3, a metal substrate having a thickness ratio t5 of the side.Fe alloy was used. In the same manner as in the i-th embodiment, the V-based low-melting point glass was used as a reference example, and Al2〇3 was used as the reference example 2. Then, according to the same method as the measurement of the thermal expansion coefficient of the first embodiment, the elongation of each of the members of Examples 14 to 18, Comparative Examples 1 and 3, and Reference Examples i and 2 was determined to be 3 (TC or more). 25 (thermal expansion coefficient in the temperature range below rc. As shown in Fig. 20, as an experimental result of the elongation measurement, the elongation (heat expansion coefficient) can be increased by increasing the thickness ratio of the 42Ni-6Cr-Fe alloy. In addition, the elongation range of the glass transition point of the V-based low melting point glass (285. The temperature range of Example 145 (12.5%) and Example 15 (25%) is less than the V-based low melting point glass. (Elongation of Reference Example 1) On the other hand, the elongations of Examples 16 to 18 and Comparative Example 3 (50% to 1%) are approximate to the elongation of the V-based low melting point glass (Reference Example 1). Further, as shown in Fig. 19 and Fig. 21, it is found that the coefficient of thermal expansion is in a temperature range of 30 ° C or more and 250 ° C or less, and the thermal expansion coefficient α 2 of Example 14 (12.5%) is 45 χ 1 〇. ·7Λ: The thermal expansion coefficient α1 (72χ10·7Λ:) is only 27% smaller than that of the V-based low melting point glass (Reference Example 1)<10 (: In addition, the thermal expansion coefficient α2 of Example 15 (25%) is 51xl (T7/°C, which is higher than the thermal expansion coefficient of the V-based low melting point glass (Reference Example 1) (72xl (T7/°c)). Only small 100142851 39 201238857 21X10 7 / ° C. That is, the metal substrate of Example 14 (12.5%) and Example 15 (25%), and V-based low melting point glass according to the sealing temperature (about 370 ° When bonding is performed at C or more and about 4 〇〇C or less, the difference in thermal expansion coefficient (α2 - αΐ) is large (27 (21 ) χ / 7 / 〇, so it is considered that the ν system is low-melting at the time of cooling. The glass layer composed of the point glass is liable to be cracked (cracked). On the other hand, in the temperature range of the above and below 250 ° C, Examples 16 to 18 and Comparative Example 3 (5〇% to 1) 〇〇%) has a coefficient of thermal expansion α2 of 58×10 /◦ or more and 74·<1〇-7/. 〇, and it is found that it is low-melting glass with ν (the thermal expansion coefficient α1 of the reference example U (72χ1 (Γ7η:)) Satisfy the relationship of -Ι4χ10_7$α2 - α1$ 2x10-7, that is, when the metal substrate of Examples 16 to 18 and the V-based low-melting glass are joined at a sealing temperature, since there is no thermal brain/service coefficient It is considered that it is possible to suppress the occurrence of cracking in the glass layer composed of the V-based low-melting glass at the time of cooling. As a result, it is considered that it is suitable to set the thickness ratio of the 42Ni-6Cr-Fe alloy to a metal substrate ( 5% or more of the cover is used as the metal substrate. It should be noted that the embodiments and examples disclosed herein are intended to be illustrative and not restrictive. The scope of the present invention is defined by the scope of the claims and the scope of the claims. For example, in the first embodiment, the metal base material 12 is an example of a 42Ni-(2 to 6)Cr-Fe alloy, and in the second embodiment, the metal base material 212 is formed. 100142851 40 201238857 first layer 212a composed of 42Ni-6Cr-Fe alloy, second layer 212b composed of 42Ni-Fe alloy, and cladding layer joined by third layer 212c composed of 42Ni-6Cr-Fe alloy The example is constituted, but the present invention is not limited to this. In the present invention, the metal material constituting the metal substrate does not need to contain Ni, and may contain Cr. In addition, in the first and second embodiments, the oxide film layers 13 (213a and 213b) mainly composed of a CoO3 film are formed in addition to the portion where the bevel nozzle 11 is disposed, but the present invention does not. Limited to this. In the present invention, the oxide film layer may be formed only in the portion where the glass layer is disposed. In the second embodiment, the metal base material 212 is an example in which three layers of cladding materials are joined by joining the first layer 212a, the second layer 212b, and the third layer 212c. However, the present invention is not limited thereto. herein. For example, it may be configured such that a first layer made of a 42Ni-6Cr-Fe alloy and a second layer of a 42Ni-Fe alloy are joined to each other. Further, it may be configured by joining four or more cladding materials. In the second embodiment, the first layer 212a and the third layer 212c are exemplified by a 42Ni-6Cr-Fe alloy having the same composition. However, 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 212a disposed on the side of the glass layer 11 is preferably about 3% by mass or more. Further, in the first and second embodiments, the glass layer 11 is an example in which a V-based low melting point including V2〇5_P2〇5-TeO-Fe203 and no Pb is formed, but the present invention is It is not limited to this. In the present invention, the glass layer is also 100142851 41 201238857, which may be a Pb-free glass material other than the V-based low melting point glass. At this time, by using a glass material which is melted at a temperature of about 400 ° C or lower, the influence of heat during sealing on the crystal oscillator can be reduced. In the above-described first embodiment and the second embodiment, the crystal vibrating reed 20 is stored in the electronic component housing case 1B, but the present invention is not limited thereto. For example, a SAW filter (surface acoustic wave filter) may be incorporated in the electronic component storage case. [Brief Description of the Drawings] Fig. 1 is a perspective view showing a configuration of a lid member for hermetic sealing according to a first embodiment of the present invention. Figure 2 is a cross-sectional view taken along line 300-300 of Figure 1. Fig. 3 is a perspective view showing the configuration of the electronic component housing case according to the first embodiment of the present invention. Figure 4 is a cross-sectional view taken along line 400-400 of Figure 3. Fig. 5 is a cross-sectional view showing a manufacturing process of the lid member for hermetic sealing according to the first embodiment of the present invention. Fig. 6 is a cross-sectional view showing a manufacturing process of the electronic component housing case according to the first embodiment of the present invention. Fig. 7 is a table showing experimental results of measurement of thermal expansion coefficient performed in order to confirm the effects of the first embodiment of the present invention. Fig. 8 is a graph showing experimental results of measurement of thermal expansion coefficient in order to confirm the effects of the first embodiment of the present invention. 100142851 42 201238857 Fig. 9 is a graph showing experimental results of measurement of thermal expansion coefficient in order to confirm the effect of the embodiment of the present invention. Fig. 10 is a table showing the results of experiments for measuring the thickness of the oxide film layer for confirming the effects of the first embodiment of the present invention. Fig. 11 is a table showing the results of experiments for measuring the thickness of the oxide film layer in order to confirm the effect of the embodiment of the present invention. Fig. 12 is a cross-sectional view showing an experimental method for measuring the wetness/interstitiality in order to confirm the effect of the embodiment of the present invention. Fig. 13 is a cross-sectional view showing an experimental method for measuring the wettability performed in order to confirm the effect of the embodiment of the present invention. Fig. 14 is a graph showing experimental results of wettability measurement performed in order to confirm the effects of the embodiment of the present invention. Fig. 15 is a graph showing the results of an experiment for measuring the wettability performed in order to confirm the effects of the embodiment of the present invention. Fig. 16 is a graph showing the results of experiments for measuring the wettability performed in order to confirm the effects of the embodiment of the present invention. Fig. 17 is a graph showing the results of an experiment for measuring the wettability performed in order to confirm the effects of the embodiment of the present invention. Fig. 8 is a cross-sectional view showing the configuration of a lid member for hermetic sealing according to a second embodiment of the present invention. The figure shows a table of experimental results of measurement of thermal expansion coefficient in order to confirm the effect of the second embodiment of the present invention.

S 100142851 43 201238857 圖20為表示為了確認本發明第2實施形態之效果而進行 之熱膨脹係數測定之實驗結果的圖表。 圖21為表示為了確認本發明第2實施形態之效果而進行 之熱膨脹係數測定之實驗結果的圖表。 【主要元件符號說明】 1 氣密密封用蓋材 2 真空爐 10 蓋 10a 上面 11 玻璃層 12 金屬基材 13 氧化皮膜層 20 水晶振藍器 30 電子零件收納構材 31 底部 32 框體 32a 上面 33 凹部 40 凸塊 100 電子零件收納用盒 110 蓋 111、111a、111b、111c 玻璃層 100142851 44 201238857 112 金屬基材 113 氧化皮膜層 114 、 114a 、 114b 、 114c 糊料 201 氣密密封用蓋材 210 蓋 212 金屬基材 212a 第1層 212b 第2層 212c 第3層 213a、213b 氧化皮膜層 tl、t2、t3、t4、t5、t6 厚度 t4a、t4b、t4c 厚度 U、L2、L3、L4 長度 W ' W1 ' W2 > W3 寬度 Wla、W2a、W3a 寬度 100142851 45S 100142851 43 201238857 Fig. 20 is a graph showing experimental results of measurement of thermal expansion coefficient in order to confirm the effects of the second embodiment of the present invention. Fig. 21 is a graph showing experimental results of measurement of thermal expansion coefficient in order to confirm the effects of the second embodiment of the present invention. [Main component symbol description] 1 Sealing material for hermetic sealing 2 Vacuum furnace 10 Cover 10a Upper surface 11 Glass layer 12 Metal substrate 13 Oxidation film layer 20 Crystal blue device 30 Electronic parts storage member 31 Bottom 32 Frame 32a Top 33 Concave 40 Bump 100 Electronic component storage case 110 Cover 111, 111a, 111b, 111c Glass layer 100142851 44 201238857 112 Metal substrate 113 Oxide film layer 114, 114a, 114b, 114c Paste 201 Sealing cover for hermetic sealing 210 212 metal substrate 212a first layer 212b second layer 212c third layer 213a, 213b oxide film layer t1, t2, t3, t4, t5, t6 thickness t4a, t4b, t4c thickness U, L2, L3, L4 length W ' W1 ' W2 > W3 Width Wla, W2a, W3a Width 100142851 45

Claims (1)

201238857 七、申請專利範圍： 1. 一種氣密密封用蓋材，係由陶瓷材料所構成，使用於含 有用於收納電子零件之電子零件收納構材的電子零件收納 用盒者； 其具備： 金屬基材，其包含至少含有Cr之金屬材料； 被覆層，係形成於上述金屬基材之表面上，由Cr之氧化 皮膜所構成；與 接合層，係形成於上述被覆層之表面上，由不含Pb之玻 璃材料所構成，且用於將形成有上述被覆層之上述金屬基材 與上述電子零件收納構材接合。 2. 如申請專利範圍第1項之氣密密封用蓋材，其中，構成 為於30°C以上且250°C以下之溫度範圍，上述接合層之熱膨 脹係數al(/°C)與上述金屬基材之熱膨脹係數a2(/°C)滿足 -15χ10·7$α2 —al$5xlCT7 的關係。 3. 如申請專利範圍第1項之氣密密封用蓋材，其中，上述 被覆層之厚度為〇.3μιη以上。 4. 如申請專利範圍第1項之氣密密封用蓋材，其中，上述 金屬基材係含有Ni、3質量％以上且6質量％以下之Cr、與 Fe的Fe系合金。 5. 如申請專利範圍第4項之氣密密封用蓋材，其中，上述 金屬基材為由42質量。/。之Ni、3質量％以上且6質量％以下 100142851 46 S 201238857 之Cr、與Fe的Fe系合金所構成。 6. 如申請專利範圍第1項之氣密密封用蓋材，其中，使上 述被覆層形成於上述接合層所配置之上述金屬基材之表面 上、及與上述接合層所配置侧為相反侧的上述金屬基材之表 面上。 7, 如申凊專利範圍第1項之氣密密封用蓋材，其中，上述 金屬基材為由至少含有配置於上述接合層側並至少含有& 之第1層、及含有與上述第！層不同之金屬材料之第2層的 包層材所構成。 8·如申請專利範圍第7項之氣密㈣用蓋材，其中，上述 第1層之熱膨脹係數大於上述接合層之熱膨脹係數，上述第 2層之熱_係數小於上述接合層之熱膨服係數。 9. 如申請專利範圍第7項之氣密密封用蓋材，其中，上述 金屬基材之上述第i層為由含有Ni、3 f量％以上且6質量 %以下之Cr、與Fe的Fe系合金所構成。 10. 如申請專利範圍第7項之氣密密封用蓋材，其中，上 述金屬基材為由含有下述層之包層材所構成： 配置於上述接合層側，至少含有&的上述第】層； ★配置於上述第丨層之與上述接合層為相反侧，含有與上述 第1層不同之金屬材料的上述第2層；與 配置於上述第2層之與上述第i層為相反側，至少含有 Cr之第3層。 S 1001428S1 47 201238857 ιι·如申請專利範圍第10項之氣密密封用蓋材，其中，上 辻弟1層及上述弟3層均為由含有Ni、3質量％以上且6質 1 /〇以下之Cr、與Fe的Fe系合金所構成。 12.如申請專利範圍第u項之氣密密封用蓋材，其中，上 述第1層及上述第3層均為由含有42質量％之Ni、6質量 %之Cr、與pe的Fe系合金所構成， 上述第2層為由含有42質量％之Ni、與Fe的Fe系合金 所構成。 13. 如申請專利範圍第u項之氣密密封用蓋材，其中，」 述第層與上述第3層的合計厚度為上述金屬基材整體厚力 的50%以上。 > 14. 一種電子零件收納用盒，係具備： 氣密密封用蓋材，其包含:金屬基材，其具有至少含Cr4 至屬材料’破覆層，係形成於上述金屬基材之表面上，^ Cr之乳化皮膜所構成；與接合層，係形成於上述被覆層《 表面上，由不含Pb之玻璃材料所構成；與 電子令件收納構材’係經由上述接合層而與形成有上述条 覆層之上述金屬基材接合，且由陶变材料所構成，用於收今 電子零件。 ' 15·如申請專利範圍第Η項之電子零件故納用盒，其中， 構成為於3代以上且：贼以下的溫度範圍中，上述接合層 之熱膨脹係數al(/t)與上述電子零件㈣構材之熱膨服: 100142851 S 48 201238857 數 a3(/°C)滿足 〇Sal —α3$1〇χ10_7 的關係。 16. 如申請專利範圍第15項之電子零件收納用盒，其中， 構成為於30°C以上且250°C以下的溫度範圍中，上述接合層 之熱膨脹係數al(/°C)與上述電子零件收納構材之熱膨脹係 數a3(/°C)滿足〇Sal —a3Sl〇xlO_7的關係，且上述接合層 之熱膨脹係數al(/°C)與上述金屬基材之熱膨脹係數a2(/°C) 滿足-15χ10·7$(χ2 —al$5xl(T7 的關係。 17. —種氣密密封用蓋材之製造方法，係用於由陶瓷材料 所構成，並含有用於收納電子零件之電子零件收納構材之電 子零件收納用盒的氣密密封用蓋材之製造方法，其具備： 於包含至少含Cr之金屬材料的金屬基材表面上，使上述 金屬基材之Cr氧化而形成由Cr之氧化皮膜所構成之被覆層 的步驟；與 於上述被覆層之表面上，形成由不含Pb之玻璃材料所構 成，且用於將形成有上述被覆層之上述金屬基材與上述電子 零件收納構材接合之接合層的步驟。 18. 如申請專利範圍第17項之氣密密封用蓋材之製造方 - 法，其中，形成上述被覆層之步驟，係包含：於含有具有含 - Ni、3質量％以上且6質量％以下之Cr、與Fe的Fe系合金 之金屬材料的上述金屬基材表面上，形成由Cr之氧化皮膜 所構成之上述被覆層的步驟。 19. 如申請專利範圍第18項之氣密密封用蓋材之製造方 s 100142851 49 201238857 法，其中，形成由Cr氧化皮膜所構成之上述被覆層的步驟， 係具有：在濕潤氫氣環境下，且l〇〇〇°C以上、1150°C以下 的溫度條件下，使上述金屬基材之Cr優先地氧化，藉此於 上述金屬基材表面上，優先形成由Cr之氧化皮膜所構成之 上述被覆層的步驟。 20.如申請專利範圍第19項之氣密密封用蓋材之製造方 法，其中，優先形成由Cr之氧化皮膜所構成之上述被覆層 的步驟，係具有：在將氧分壓設定為小於可將Fe及Ni氧化 之分壓、且大於可將Cr氧化之分壓的上述濕潤氫氣環境 下’優先形成由Cr之氧化皮膜所構成之上述被覆層的步驟。 100142851 50201238857 VII. Patent application scope: 1. A cover material for hermetic sealing, which is composed of a ceramic material and used in an electronic component storage box containing an electronic component storage member for accommodating electronic components; a substrate comprising a metal material containing at least Cr; a coating layer formed on the surface of the metal substrate and composed of an oxide film of Cr; and a bonding layer formed on the surface of the coating layer, The Pb-containing glass material is used to bond the metal substrate on which the coating layer is formed to the electronic component storage member. 2. The lid member for hermetic sealing according to the first aspect of the invention, wherein the bonding layer has a thermal expansion coefficient a (/° C.) and the metal in a temperature range of 30 ° C or more and 250 ° C or less The thermal expansion coefficient a2 (/°C) of the substrate satisfies the relationship of -15χ10·7$α2 —al$5xlCT7. 3. The cover sheet for hermetic sealing according to the first aspect of the invention, wherein the thickness of the coating layer is 〇.3 μmη or more. 4. The cover material for a hermetic seal according to the first aspect of the invention, wherein the metal base material contains Ni, 3% by mass or more and 6% by mass or less of Cr, and Fe-based alloy with Fe. 5. The cover material for hermetic sealing according to item 4 of the patent application, wherein the metal substrate is 42 mass. /. Ni, 3% by mass or more and 6% by mass or less 100142851 46 S 201238857 Cr, Fe alloy with Fe. 6. The cover sheet for hermetic sealing according to the first aspect of the invention, wherein the coating layer is formed on a surface of the metal substrate disposed on the bonding layer and on a side opposite to a side on which the bonding layer is disposed On the surface of the above metal substrate. 7. The sealing material for hermetic sealing according to the first aspect of the invention, wherein the metal substrate comprises at least a first layer disposed on the side of the bonding layer and containing at least & It is composed of a cladding material of the second layer of a metal material having different layers. 8. The airtight (4) cover material according to item 7 of the patent application scope, wherein the thermal expansion coefficient of the first layer is greater than the thermal expansion coefficient of the bonding layer, and the thermal coefficient of the second layer is smaller than the thermal expansion of the bonding layer coefficient. 9. The cover sheet for hermetic sealing according to the seventh aspect of the invention, wherein the ith layer of the metal substrate is made of Ni, 3 % by weight or more and 6% by mass or less of Cr, and Fe of Fe. It is composed of an alloy. 10. The cover sheet for hermetic sealing according to claim 7, wherein the metal base material is composed of a clad material having a layer which is disposed on the side of the joint layer and contains at least the above a second layer disposed on the opposite side of the bonding layer opposite to the bonding layer and containing a metal material different from the first layer; and the second layer disposed opposite to the second layer The side contains at least the third layer of Cr. S 1001428S1 47 201238857 PCT Patent Application No. 10 of the patent application, the first and second layers of the above-mentioned patents, including the Ni, the 3% by mass or more, and the It consists of Cr and a Fe-based alloy of Fe. 12. The lid member for hermetic sealing according to the invention of claim 5, wherein the first layer and the third layer are each a Fe-based alloy containing 42% by mass of Ni, 6% by mass of Cr, and pe. In this configuration, the second layer is made of a Fe-based alloy containing 42% by mass of Ni and Fe. 13. The cover sheet for hermetic sealing according to the invention of claim 5, wherein the total thickness of the first layer and the third layer is 50% or more of the total thickness of the metal substrate. < 14. An electronic component storage case comprising: a cover material for hermetic sealing, comprising: a metal base material having at least a Cr4-containing material-breaking layer formed on a surface of the metal substrate The emulsified film of ^Cr is formed; and the bonding layer is formed on the surface of the coating layer "the surface is made of a glass material containing no Pb; and the electronic component accommodating member" is formed by the bonding layer. The above-mentioned metal substrate having the above-mentioned strip coating is joined and composed of a ceramic material, and is used for receiving electronic parts. '15. The electronic component use box according to the third aspect of the patent application, wherein the thermal expansion coefficient a(/t) of the bonding layer and the electronic component are in a temperature range of three or more generations and less than a thief (4) Thermal expansion of the member material: 100142851 S 48 201238857 The number a3 (/°C) satisfies the relationship of 〇Sal_α3$1〇χ10_7. 16. The electronic component storage case according to claim 15, wherein the thermal expansion coefficient a (/° C.) of the bonding layer is in a temperature range of 30° C. or more and 250° C. or less The thermal expansion coefficient a3 (/° C.) of the component storage member satisfies the relationship of 〇Sal — a3Sl 〇 xlO_7, and the thermal expansion coefficient a (/° C.) of the bonding layer and the thermal expansion coefficient a2 (/° C.) of the above metal substrate. Meets -15χ10·7$(χ2—al$5xl (T7 relationship. 17. A method for manufacturing a hermetic sealing cover material, which is used for ceramic materials and contains electronic parts for accommodating electronic parts. A method for producing a lid member for hermetic sealing of an electronic component storage case containing a member, comprising: oxidizing Cr of the metal substrate to form a Cr on a surface of a metal substrate including a metal material containing at least Cr; a step of forming a coating layer formed by the oxide film; forming a glass material containing no Pb on the surface of the coating layer, and accommodating the metal substrate on which the coating layer is formed and the electronic component Material-bonded joint layer The method for producing a cover sheet for hermetic sealing according to claim 17, wherein the step of forming the coating layer comprises: containing -Ni, 3% by mass or more and 6 mass a step of forming the above-mentioned coating layer composed of an oxide film of Cr on the surface of the metal substrate of Cr or a metal material of Fe-based alloy with Fe. The hermetic seal of claim 18 The method for producing the above-mentioned coating layer composed of a Cr oxide film by the method of manufacturing a cover material, wherein the method of forming the coating layer composed of the Cr oxide film is in a humid hydrogen atmosphere, and is not more than 10 ° C and not more than 1150 ° C. Under the temperature condition, the Cr of the metal substrate is preferentially oxidized, thereby preferentially forming the coating layer composed of the oxide film of Cr on the surface of the metal substrate. 20. Patent Application No. 19 The method for producing a cover material for hermetic sealing, wherein the step of preferentially forming the coating layer composed of an oxide film of Cr has a step of setting the oxygen partial pressure to be less than Fe and Ni oxygen A step of dividing, and may be greater than the wet hydrogen atmosphere under partial pressure of the oxidation of Cr 'preferential formation of the coating layer of an oxide film formed of the Cr. 10014285150
TW100142851A 2011-02-07 2011-11-23 A method for manufacturing a cover for a hermetic seal, an electronic component storage case, and a sealing material for hermetic sealing TWI516423B (en)

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TWI581341B (en) * 2014-10-30 2017-05-01 Hitachi Metals Ltd And a method for manufacturing the same, and an electronic component storage package
TWI686968B (en) * 2015-02-26 2020-03-01 日商日本電氣硝子股份有限公司 Airtight package and its manufacturing method

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EP2919263B1 (en) * 2012-11-12 2021-08-18 Hitachi Metals, Ltd. Cover material for hermetic sealing of a package
JP6485020B2 (en) 2014-12-02 2019-03-20 日立金属株式会社 Glass bonding material and multi-layer glass
DE102019119961A1 (en) 2019-07-24 2021-01-28 Schott Ag Hermetically sealed, transparent cavity and its housing
CN113328725B (en) * 2021-05-21 2024-04-05 武汉衍熙微器件有限公司 Acoustic wave resonant structure, filter and method for manufacturing acoustic wave resonant structure

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CN100365803C (en) * 2003-02-06 2008-01-30 株式会社新王材料 Hermetic sealing cap and method for producing same
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WO2017057406A1 (en) * 2015-09-28 2017-04-06 リンテック株式会社 Adhesive sheet and method for producing adhesive sheet

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TWI581341B (en) * 2014-10-30 2017-05-01 Hitachi Metals Ltd And a method for manufacturing the same, and an electronic component storage package
TWI686968B (en) * 2015-02-26 2020-03-01 日商日本電氣硝子股份有限公司 Airtight package and its manufacturing method

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