TWI606882B - Substrate with solder and method of manufacturing the same - Google Patents

Substrate with solder and method of manufacturing the same Download PDF

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TWI606882B
TWI606882B TW103128949A TW103128949A TWI606882B TW I606882 B TWI606882 B TW I606882B TW 103128949 A TW103128949 A TW 103128949A TW 103128949 A TW103128949 A TW 103128949A TW I606882 B TWI606882 B TW I606882B
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solder
substrate
vicinity
ratio
base material
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TW103128949A
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TW201524660A (en
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仁科順矢
淺田賢
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日立金屬股份有限公司
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/161Cap
    • H01L2924/1615Shape
    • H01L2924/16195Flat cap [not enclosing an internal cavity]

Description

具焊料基材及具焊料基材之製造方法 Solder substrate and method of manufacturing solder substrate

本發明係關於具焊料基材及具焊料基材之製造方法,特別係關於具備至少含有Ag與Cu之焊料的具焊料基材、及該具焊料基材之製造方法。 The present invention relates to a method for producing a solder substrate and a solder substrate, and more particularly to a solder substrate having a solder containing at least Ag and Cu, and a method of manufacturing the solder substrate.

習知已知有具備至少含有Ag(銀)與Cu(銅)之焊料的具焊料基材。此種具焊料基材例如日本專利特開2006-49595號公報中有揭示。 A solder substrate having a solder containing at least Ag (silver) and Cu (copper) is known. Such a solder-based substrate is disclosed, for example, in Japanese Laid-Open Patent Publication No. 2006-49595.

日本專利特開2006-49595號公報所揭示的焊料覆蓋材,係包括有:由金屬構成的基材;以及由Ag-Cu-Sn(錫)合金、Ag-Cu-In(銦)合金或Ag-Cu-Zn(鋅)合金構成,且接合於基材表面的焊料層。 The solder coating material disclosed in Japanese Laid-Open Patent Publication No. 2006-49595 includes: a substrate made of a metal; and an Ag-Cu-Sn (tin) alloy, an Ag-Cu-In (indium) alloy, or Ag. a solder layer composed of a Cu-Zn (zinc) alloy and bonded to the surface of the substrate.

然而,日本專利特開2006-49595號公報所記載的焊料覆蓋材,當長期間保管的情況、或配置於高溫多濕環境下的情況等,較焊料層中所含Ag具更高離子化傾向的元素,會與空氣中的氧及水分、以及由氯化物離子等陰離子等所構成的外部腐蝕因子產生反應並腐蝕。特別係至少含有Ag與Cu的焊料,相較於Ag、Cu之外,因為其他的Sn等所佔比例(質量%)較小,因而在焊料層表面會大量生成由較Ag具更高離子化傾向的Cu腐蝕所造成的腐蝕生 成物。所以,藉由將表面有存在Cu系腐蝕生成物的焊料覆蓋材之焊料予以熔解,將基材接著於其他構件,而密封其他構件時,會成為接著部混雜有腐蝕生成物的狀態,導致因接著不良造成的滲漏不良率(leakage defectives)增加(即密封性降低)的問題。 However, the solder coating material described in Japanese Laid-Open Patent Publication No. 2006-49595 has a higher ionization tendency than the Ag contained in the solder layer when stored for a long period of time or when placed in a high-temperature and high-humidity environment. The element reacts with and corrodes with oxygen and moisture in the air and external corrosion factors such as anions such as chloride ions. In particular, a solder containing at least Ag and Cu has a larger proportion (% by mass) of other Sns than Ag and Cu, and thus a large amount of ionization is formed on the surface of the solder layer. Corrosion caused by tendency to Cu corrosion Adult. Therefore, by melting the solder of the solder coating material having the Cu-based corrosion product on the surface, the substrate is bonded to the other member, and when the other member is sealed, the corrosion product is mixed in the succeeding portion, resulting in Then, the problem of increased leakage defectives (i.e., reduced sealing property) caused by the failure is caused.

本發明係為解決如上述問題而完成,本發明之一目的係提供:能抑制在至少含有Ag與Cu之焊料表面,生成腐蝕生成物的具焊料基材及該具焊料基材之製造方法。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a solder substrate and a method for producing the solder substrate which can suppress a surface of a solder containing at least Ag and Cu to form a corrosion product.

本案發明者經深入鑽研的結果,發現藉由著眼於焊料表面、或其附近區域的Ag含有質量比率,而可解決上述問題。 As a result of intensive research, the inventors of the present invention have found that the above problem can be solved by focusing on the mass ratio of Ag on the surface of the solder or the vicinity thereof.

即,根據本發明第1態樣的具焊料基材,係具備有:基材、以及形成於基材上且至少含有Ag與Cu的焊料;其中,焊料中Ag含有質量相對於Ag與Cu合計的比率為0.95以上之表面附近區域,係形成於從焊料表面起朝深度方向至1.3μm以上深度處。另外,所謂「表面附近區域」係指由焊料表面、以及從焊料表面起朝深度方向至既定長度的區域等二者構成的區域。 In other words, the solder base material according to the first aspect of the present invention includes: a base material; and a solder formed on the base material and containing at least Ag and Cu; wherein the mass of Ag in the solder is equal to Ag and Cu. The region near the surface having a ratio of 0.95 or more is formed from the surface of the solder toward the depth direction to a depth of 1.3 μm or more. In addition, the "area in the vicinity of the surface" means a region composed of both the surface of the solder and the region from the surface of the solder toward the depth direction to a predetermined length.

根據本發明第1態樣的具焊料基材,如上述,具備有Ag含有質量相對於Ag與Cu合計的比率為0.95以上的表面附近區域。藉此,在容易與外部腐蝕因子產生反應的焊料表面附近區域,因為具有較Cu更低離子化傾向且耐蝕性較高的Ag含有質量比率充分變大,因而相對的較Ag更高離子化傾向且耐蝕性較低的Cu含有質量比率充分變小,結果可充分抑制外部腐蝕因子與Cu在焊料表面附近區域的反應。又,根據本發明第1態樣的具焊料基材,具備有表面附近區域係從焊料表面起朝深度方向至1.3μm以上深度 處。藉此,從焊料表面起至充分深度處為止可形成較不易受外部腐蝕因子影響的狀態,因而可抑制外部腐蝕因子與Cu在焊料表面附近區域的反應。藉由該等,可抑制在焊料的表面附近區域產生腐蝕生成物情形。另外,該等效果經實驗確認完成。此項結果可抑制因腐蝕生成物造成的變色而導致具焊料基材的外觀感覺變差情形,以及當將具焊料基材使用為電子零件收納用包裝的密封構件時,可抑制接著部混雜有腐蝕生成物情形,故可抑制因接著不良而造成的滲漏不良率增加,結果可抑制具焊料基材(密封構件)的密封性降低。 又,若具有上述構成的具焊料基材,在焊料表面附近區域以外的內部區域,因為Ag含有質量比率不需要為0.95以上,因而可抑制焊料自身的Ag含有量,結果可抑制焊料熔點提高,且可降低屬於貴金屬的Ag使用量。 According to the solder base material of the first aspect of the present invention, as described above, the vicinity of the surface having a ratio of the Ag-containing mass to the total of Ag and Cu of 0.95 or more is provided. Thereby, in the vicinity of the surface of the solder which is likely to react with the external corrosion factor, since the Ag-containing mass ratio which is lower in ionization tendency than Cu and which has higher corrosion resistance is sufficiently larger, the relative Ag is more ionized than the Ag. Further, the Cu-containing mass ratio having a low corrosion resistance is sufficiently small, and as a result, the reaction of the external corrosion factor with Cu in the vicinity of the solder surface can be sufficiently suppressed. Further, according to the first aspect of the present invention, the solder substrate is provided with a region in the vicinity of the surface from the solder surface to a depth of 1.3 μm or more. At the office. Thereby, a state which is less susceptible to external corrosion factors can be formed from the surface of the solder to a sufficient depth, and thus the reaction of the external corrosion factor with Cu in the vicinity of the solder surface can be suppressed. By this, it is possible to suppress the occurrence of corrosion products in the vicinity of the surface of the solder. In addition, these effects were confirmed by experiments. As a result of this, it is possible to suppress the deterioration of the appearance of the solder substrate due to the discoloration caused by the corrosion product, and to suppress the adhesion of the succeeding portion when the solder substrate is used as the sealing member of the electronic component storage package. In the case of the corrosion product, it is possible to suppress an increase in the leakage failure rate due to the subsequent failure, and as a result, it is possible to suppress a decrease in the sealing property of the solder base material (sealing member). In addition, in the internal region other than the region near the surface of the solder, the Ag-containing mass ratio does not need to be 0.95 or more, so that the Ag content of the solder itself can be suppressed, and as a result, the melting point of the solder can be suppressed. And it can reduce the amount of Ag used in precious metals.

根據上述第1態樣的具焊料基材,較佳焊料中,Ag含有質量相對於Ag與Cu合計的比率(即Ag/(Ag+Cu)),係較大於Cu含有質量相對於Ag與Cu合計的比率(即Cu/(Ag+Cu))。若依此構成,例如焊料表面附近區域的Cu會優先除去,當欲使表面附近區域的Ag含有質量比率達0.95以上的情況,藉由在優先除去Cu之前的焊料Ag含有質量比率較大於Cu含有質量比率,可輕易地形成使焊料表面附近區域的Ag含有質量比率為0.95以上。此處,為提高焊料表面附近區域的Ag含有質量比率,Ag含有質量相對於Ag與Cu合計的比率若達Cu含有質量對Ag與Cu合計的比率之1.5倍以上,則可輕易地提高Ag含有質量比率,故屬較佳,更佳係2倍以上,特別係若達4倍以上,則可特別輕易地提高Ag含有質量比率。 According to the solder substrate of the first aspect described above, in the solder, the ratio of the Ag content to the total of Ag and Cu (i.e., Ag/(Ag+Cu)) is larger than the Cu content with respect to Ag and Cu. The ratio is total (ie Cu/(Ag+Cu)). According to this configuration, for example, Cu in the vicinity of the surface of the solder is preferentially removed, and when the mass ratio of Ag in the vicinity of the surface is desired to be 0.95 or more, the mass ratio of the solder Ag before the Cu is preferentially removed is larger than that of the Cu. The mass ratio can be easily formed so that the Ag content ratio in the vicinity of the solder surface is 0.95 or more. Here, in order to increase the mass ratio of Ag contained in the vicinity of the surface of the solder, the ratio of the Ag-containing mass to the total of Ag and Cu is 1.5 times or more the ratio of the Cu-containing mass to the total of Ag and Cu, and the Ag content can be easily increased. The mass ratio is preferred, and more preferably more than 2 times, and particularly if it is more than 4 times, the Ag content ratio can be particularly easily increased.

根據上述第1態樣的具焊料基材,較佳焊料全體的Ag含有質量比率係0.64以上。若依此構成,例如焊料表面附近區域的Cu會優先除去,當欲使表面附近區域的Ag含有質量比率成為0.95以上的情況,可更輕易地形成焊料表面附近區域的Ag含有質量比率為0.95以上。 According to the solder base material of the first aspect described above, it is preferable that the Ag contains a mass ratio of 0.64 or more. According to this configuration, for example, Cu in the vicinity of the surface of the solder is preferentially removed, and when the mass ratio of Ag in the vicinity of the surface is desired to be 0.95 or more, the Ag content ratio in the vicinity of the solder surface can be more easily formed to be 0.95 or more. .

根據上述第1態樣的具焊料基材,較佳焊料全體的Ag含有質量比率係0.85以下。若依此構成,可抑制焊料全體中的Ag含有質量比率過度提高,因而可抑制焊料全體的熔點過度提高。藉此可抑制焊接溫度提高。 According to the solder base material of the first aspect described above, it is preferable that the Ag content of the entire solder contains a mass ratio of 0.85 or less. According to this configuration, it is possible to suppress an excessive increase in the mass ratio of Ag contained in the entire solder, and it is possible to suppress an excessive increase in the melting point of the entire solder. Thereby, the soldering temperature can be suppressed from increasing.

根據上述第1態樣的具焊料基材,較佳係由基材與焊料相互接合而形成的覆蓋材。若依此構成,藉由基材與焊料進行接合,可抑制腐蝕因子滲入基材與焊料的界面處。藉此,不僅焊料表面,就連基材與焊料的界面處亦能抑制生成腐蝕生成物,因而可抑制基材與焊料發生分離情形。結果,可更加提升具焊料基材的可靠度。 The solder base material according to the first aspect described above is preferably a cover material formed by bonding a base material and a solder to each other. According to this configuration, by bonding the substrate to the solder, it is possible to suppress the penetration of the corrosion factor into the interface between the substrate and the solder. Thereby, not only the surface of the solder but also the interface between the substrate and the solder can suppress the formation of corrosion products, thereby suppressing the separation of the substrate from the solder. As a result, the reliability of the solder substrate can be further improved.

根據上述第1態樣的具焊料基材,較佳係使用為電子零件收納用包裝的密封環。依此使用為密封環的具焊料基材,藉由Ag含有質量比率為0.95以上的表面附近區域,係從焊料表面朝深度方向形成至1.3μm以上深度,而可抑制密封環的焊料表面附近區域生成腐蝕生成物情形。 According to the solder base material of the first aspect described above, it is preferable to use a seal ring which is a package for electronic component storage. According to this, the solder base material which is a seal ring is used, and the region near the surface having a mass ratio of 0.95 or more is formed from the solder surface toward the depth direction to a depth of 1.3 μm or more, and the vicinity of the solder surface of the seal ring can be suppressed. A corrosion product is generated.

根據上述第1態樣的具焊料基材,較佳係使用為電子零件收納用包裝的蓋材。依此使用為蓋材的具焊料基材,藉由Ag含有質量比率為0.95以上的表面附近區域,係從焊料表面朝深度方向形成至1.3μm以上深度,而可抑制蓋材的焊料表面附近區域生成 腐蝕生成物情形。 According to the solder base material of the first aspect described above, it is preferable to use a cover material which is a package for electronic component storage. In this case, the solder-containing substrate which is a cover material is used, and the region near the surface having a mass ratio of 0.95 or more is formed from the solder surface toward the depth direction to a depth of 1.3 μm or more, and the vicinity of the solder surface of the cover material can be suppressed. generate Corrosion product situation.

根據上述第1態樣的具焊料基材,較佳焊料係含有Ag、Cu及Sn,且焊料的Sn含有率係6質量%以下。若依此構成,利用焊料中所含有的Sn,可輕易地抑制焊接溫度提高情形。又,藉由焊料的Sn含有率設定在6質量%以下,可抑制製作具焊料基材時的加工性降低情形。特別係當將基材與焊料進行接合而製作覆蓋材時,可抑制軋延趨於困難情形。 In the solder base material according to the first aspect described above, it is preferable that the solder contains Ag, Cu, and Sn, and the Sn content of the solder is 6% by mass or less. According to this configuration, it is possible to easily suppress the improvement of the soldering temperature by using Sn contained in the solder. In addition, when the Sn content of the solder is set to 6 mass% or less, it is possible to suppress a decrease in workability when a solder substrate is produced. In particular, when a substrate and a solder are joined to form a cover material, it is possible to suppress the rolling from becoming difficult.

根據上述第1態樣的具焊料基材,較佳表面附近區域係沿焊料表面全域形成。若依此構成,可抑制沿焊料表面全域生成腐蝕生成物。 According to the solder substrate of the first aspect described above, it is preferred that the vicinity of the surface be formed along the entire surface of the solder surface. According to this configuration, generation of corrosion products along the entire surface of the solder can be suppressed.

根據上述第1態樣的具焊料基材,較佳表面附近區域係從焊料表面朝深度方向形成至1.5μm以上深度處。若依此構成,可形成從焊料表面起至充分深度處均呈不易受外部腐蝕因子影響的狀態,因而可更加抑制外部腐蝕因子與Cu在焊料表面附近區域產生反應。藉此可更加抑制在焊料表面附近區域生成腐蝕生成物情形。 According to the solder substrate of the first aspect described above, it is preferable that the region near the surface is formed from the solder surface toward the depth direction to a depth of 1.5 μm or more. According to this configuration, it is possible to form a state in which it is less susceptible to external corrosion factors from the surface of the solder to a sufficient depth, and thus it is possible to further suppress the reaction between the external corrosion factor and Cu in the vicinity of the solder surface. Thereby, it is possible to further suppress the occurrence of a corrosion product in the vicinity of the solder surface.

此情況,較佳表面附近區域係從焊料表面起朝深度方向形成至2.0μm以上深度處。若依此構成,可從焊料表面起至更充分深度處均呈不易受外部腐蝕因子影響的狀態,因而可有效地抑制外部腐蝕因子與Cu在焊料表面附近區域產生反應。藉此可有效地抑制在焊料表面附近區域生成腐蝕生成物情形。 In this case, it is preferable that the vicinity of the surface is formed in the depth direction from the solder surface to a depth of 2.0 μm or more. According to this configuration, it is possible to be in a state in which it is less susceptible to external corrosion factors from the surface of the solder to a deeper depth, and thus it is possible to effectively suppress the reaction of the external corrosion factor with Cu in the vicinity of the solder surface. Thereby, it is possible to effectively suppress the occurrence of a corrosion product in the vicinity of the surface of the solder.

根據上述第1態樣的具焊料基材,較佳表面附近區域係從焊料表面起朝深度方向形成至4.0μm以下深度。若依此構成,Ag含有質量比率會提高,結果可抑制熔點較高的表面附近區域之 深度過度增加,故可抑制焊料全體的熔點過度提高。藉此可抑制焊接溫度提高。 According to the solder substrate of the first aspect described above, it is preferable that the region near the surface is formed to a depth of 4.0 μm or less from the surface of the solder in the depth direction. According to this configuration, the Ag-containing mass ratio is increased, and as a result, the vicinity of the surface having a higher melting point can be suppressed. Since the depth is excessively increased, it is possible to suppress an excessive increase in the melting point of the entire solder. Thereby, the soldering temperature can be suppressed from increasing.

根據上述第1態樣的具焊料基材,較佳在基材的焊料側形成含Cu之應力緩和層。若依此構成,藉由具柔軟性之含Cu應力緩和層,可吸收因焊料與基材間之熱膨脹差所造成的熱應力與應變,俾可抑制在熔接地方(焊接)附近發生剝離等情形。又,藉由應力緩和層含有Cu,而可提升應力緩和層的熱傳導性,所以可有效率地傳導熔接地方附近的熱。藉此,可抑制熔接地方附近的熱應力變大。 According to the solder substrate of the first aspect described above, it is preferable to form a stress relaxation layer containing Cu on the solder side of the substrate. According to this configuration, the soft Cu-containing stress relaxation layer absorbs thermal stress and strain caused by the difference in thermal expansion between the solder and the substrate, and the occurrence of peeling in the vicinity of the welded portion (welding) can be suppressed. . Further, since the stress relaxation layer contains Cu, the thermal conductivity of the stress relaxation layer can be improved, so that heat in the vicinity of the welded portion can be efficiently conducted. Thereby, it is possible to suppress an increase in thermal stress in the vicinity of the welded portion.

根據本發明第2態樣的具焊料基材之製造方法,係包括有:對基材上所形成至少含有Ag與Cu的焊料,使用含有為優先除去Cu之優先除銅劑的蝕刻液,施行濕式蝕刻的步驟;其中,藉由在濕式蝕刻中,利用蝕刻液的優先除銅劑,優先除去焊料表面附近區域的Cu,使Ag含有質量對Ag與Cu合計的比率達0.95以上的表面附近區域,從焊料表面朝深度方向形成至1.3μm以上深度處。 A method for producing a solder substrate according to a second aspect of the present invention includes: forming an solder containing at least Ag and Cu on a substrate, using an etching solution containing a preferential copper removing agent which preferentially removes Cu; a step of wet etching; wherein, by using a preferential copper removal agent of the etching solution in the wet etching, Cu in a region near the surface of the solder is preferentially removed, so that the Ag contains a surface having a mass ratio of Ag to Cu of 0.95 or more The vicinity is formed from the solder surface toward the depth direction to a depth of 1.3 μm or more.

根據本發明第2態樣的具焊料基材之製造方法,如上述,形成Ag含有質量對Ag與Cu合計的比率為0.95以上的表面附近區域。藉此,在較容易與外部腐蝕因子產生反應的焊料表面附近區域中,較Cu更低離子化傾向且耐蝕性較高的Ag含有質量比率充分變大,相對的較Ag更高離子化傾向且耐蝕性較低的Cu含有質量比率充分變小,結果可充分抑制外部腐蝕因子與Cu在焊料表面附近區域處產生反應。又,根據本發明第2態樣的具焊料基材之製造方法,表面附近區域係形成從焊料表面起朝深度方向至 1.3μm以上深度處。藉此,從焊料表面起至充分深度處為止可形成較不易受外部腐蝕因子影響的狀態,因而可抑制外部腐蝕因子與Cu在焊料表面附近區域的反應。藉由該等,可抑制在焊料的表面附近區域產生腐蝕生成物情形。此項結果可抑制因腐蝕生成物造成的變色而導致具焊料基材的外觀感覺變差情形,以及當將具焊料基材使用為電子零件收納用包裝的密封構件時,可抑制接著部混雜有腐蝕生成物情形,故可抑制因接著不良而造成的滲漏不良率增加,結果可抑制具焊料基材(密封構件)的密封性降低。又,根據上述具焊料基材之製造方法,在焊料附近區域以外的內部區域,因為Ag含有質量比率不需要為0.95以上,因而可抑制焊料自身的Ag含有量,結果可抑制焊料熔點提高,且可降低屬於貴金屬的Ag使用量。 又,濕式蝕刻中,藉由利用蝕刻液的優先除銅劑,優先除去焊料表面附近區域的Cu,而該被除去的Cu份量可輕易地使焊料表面附近區域的Ag含有質量比率增加。 According to the method for producing a solder substrate according to the second aspect of the present invention, as described above, a region in the vicinity of the surface in which the ratio of the Ag-containing mass to the total of Ag and Cu is 0.95 or more is formed. Therefore, in the vicinity of the surface of the solder which is more likely to react with the external corrosion factor, the Ag-containing mass ratio which is lower in ionization tendency and higher in corrosion resistance than Cu is sufficiently increased, and the relative Ag is more ionized than Ag and The Cu-containing mass ratio having a low corrosion resistance is sufficiently small, and as a result, the external corrosion factor can be sufficiently suppressed to react with Cu at a region near the surface of the solder. Further, according to the manufacturing method of the solder substrate of the second aspect of the present invention, the vicinity of the surface is formed from the solder surface toward the depth direction to Above 1.3μm depth. Thereby, a state which is less susceptible to external corrosion factors can be formed from the surface of the solder to a sufficient depth, and thus the reaction of the external corrosion factor with Cu in the vicinity of the solder surface can be suppressed. By this, it is possible to suppress the occurrence of corrosion products in the vicinity of the surface of the solder. As a result of this, it is possible to suppress the deterioration of the appearance of the solder substrate due to the discoloration caused by the corrosion product, and to suppress the adhesion of the succeeding portion when the solder substrate is used as the sealing member of the electronic component storage package. In the case of the corrosion product, it is possible to suppress an increase in the leakage failure rate due to the subsequent failure, and as a result, it is possible to suppress a decrease in the sealing property of the solder base material (sealing member). Further, according to the method for producing a solder substrate, the Ag-containing mass ratio does not need to be 0.95 or more in the internal region other than the region in the vicinity of the solder, so that the Ag content of the solder itself can be suppressed, and as a result, the melting point of the solder can be suppressed from being improved. It can reduce the amount of Ag used in precious metals. Further, in the wet etching, Cu is preferentially removed by the preferential copper removal agent of the etching liquid, and the amount of removed Cu can easily increase the Ag content ratio in the vicinity of the solder surface.

根據上述第2態樣的具焊料基材之製造方法,較佳優先除銅劑係含有強酸。若依此構成,可使離子化傾向較高於Ag的Cu之氧化物等Cu化合物,輕易地溶解於強酸中,另一方面,離子化傾向較低於Cu的Ag則不易溶解於強酸中,因而可確實地從焊料表面附近區域優先地除去Cu。 According to the method for producing a solder substrate according to the second aspect described above, it is preferable that the copper removal agent contains a strong acid. According to this configuration, a Cu compound such as an oxide of Cu having a higher ionization tendency than Ag can be easily dissolved in a strong acid, and on the other hand, Ag having a lower ionization tendency than Cu is less likely to be dissolved in a strong acid. Therefore, Cu can be preferentially removed from the vicinity of the solder surface.

此情況,較佳優先除銅劑係含有屬於強酸的硫酸。若依此構成,會生成屬於硫酸之陰離子的硫酸陰離子與Cu陽離子的化合物(硫酸銅),因為所生成的化合物係呈水溶性,即可溶於蝕刻液中,因而焊料表面與表面附近區域的Cu之氧化物等Cu化合物等等會利用強酸而溶解,俾可抑制蝕刻液內析出Cu化合物並附著於 具焊料基材。藉此,因為不需要設計將所附著析出物從具焊料基材除去的步驟,因而可成為簡單的具焊料基材之製造步驟。 In this case, it is preferred that the copper removal agent contains sulfuric acid which is a strong acid. According to this configuration, a compound of a sulfate anion and a Cu cation (copper sulfate) which is an anion of sulfuric acid is formed, since the resulting compound is water-soluble and can be dissolved in the etching liquid, and thus the surface of the solder and the vicinity of the surface A Cu compound such as an oxide of Cu or the like is dissolved by a strong acid, and the Cu compound is inhibited from being precipitated in the etching liquid and adhered thereto. With solder substrate. Thereby, since it is not necessary to design a step of removing the deposited precipitate from the solder substrate, it can be a simple manufacturing step of the solder substrate.

根據上述第2態樣的具焊料基材之製造方法,較佳在施行濕式蝕刻的步驟之前,更進一步包括有使用研磨材施行研磨的步驟,例如滾筒研磨等步驟。若依此構成,例如利用沖孔等機械加工而形成的具焊料基材,因為利用濕式蝕刻無法輕易除去的毛邊、異物等可預先被除去,因而只要在濕式蝕刻中,調整焊料表面附近區域成為能獲得本發明作用效果之既定狀態的處理條件即可,結果可使具焊料基材之製造步驟簡單化。 According to the second aspect of the method for producing a solder substrate, it is preferable to further include a step of performing polishing using an abrasive material, such as barrel polishing, before the step of performing the wet etching. According to this configuration, for example, a solder base material formed by machining such as punching can be removed in advance because burrs, foreign matter, and the like which cannot be easily removed by wet etching can be removed in advance, so that the wet soldering surface is adjusted in the vicinity of the solder surface. The region may be a processing condition in which a predetermined state of the effect of the present invention can be obtained, and as a result, the manufacturing step of the solder substrate can be simplified.

根據上述第2態樣的具焊料基材之製造方法,較佳焊料中,Ag含有質量相對於Ag與Cu合計的比率,係較大於Cu含有質量相對於Ag與Cu合計的比率。若依此構成,可輕易地形成焊料表面附近區域的Ag含有質量比率為0.95以上。 According to the method for producing a solder substrate according to the second aspect described above, in the solder, the ratio of the Ag-containing mass to the total of Ag and Cu is larger than the ratio of the Cu-containing mass to the total of Ag and Cu. According to this configuration, the Ag content ratio in the vicinity of the solder surface can be easily formed to be 0.95 or more.

根據上述第2態樣的具焊料基材之製造方法,較佳焊料全體的Ag含有質量比率係0.64以上。若依此構成,可更輕易地形成焊料表面附近區域的Ag含有質量比率為0.95以上。 According to the method for producing a solder substrate according to the second aspect described above, it is preferable that the Ag contains a mass ratio of 0.64 or more. According to this configuration, the Ag content ratio in the vicinity of the solder surface can be more easily formed to be 0.95 or more.

根據上述第2態樣的具焊料基材之製造方法,較佳在施行濕式蝕刻的步驟之前,更進一步包括有利用基材與焊料相互接合而形成覆蓋材的步驟。若依此構成,藉由基材與焊料相接合,而可抑制在基材與焊料的界面處滲入腐蝕因子。藉此,不僅焊料表面,基材與焊料的界面處亦可抑制腐蝕生成物生成,因而可抑制基材與焊料發生分離情形。結果可更加提升具焊料基材的可靠度。 According to the second aspect of the method of manufacturing a solder substrate, it is preferable to further include a step of forming a cover material by bonding the substrate and the solder to each other before the step of performing the wet etching. According to this configuration, by bonding the substrate to the solder, it is possible to suppress penetration of the corrosion factor at the interface between the substrate and the solder. Thereby, not only the surface of the solder but also the interface between the substrate and the solder can suppress the formation of corrosion products, thereby suppressing the separation of the substrate from the solder. As a result, the reliability of the solder substrate can be further improved.

1、201a、201b‧‧‧密封環 1, 201a, 201b‧‧‧ seal ring

1a‧‧‧上面 1a‧‧‧above

1d‧‧‧微小突起 1d‧‧‧ tiny protrusions

2‧‧‧異物 2‧‧‧ Foreign objects

10‧‧‧基材 10‧‧‧Substrate

11‧‧‧Ni層 11‧‧‧Ni layer

12‧‧‧中間層 12‧‧‧Intermediate

13‧‧‧Cu層 13‧‧‧Cu layer

20‧‧‧焊料 20‧‧‧ solder

20a、120a‧‧‧表面 20a, 120a‧‧‧ surface

21‧‧‧表面附近區域 21‧‧‧The area near the surface

22‧‧‧內部區域 22‧‧‧Internal area

100、200‧‧‧電子零件收納用包裝 100,200‧‧‧Package for electronic parts storage

101‧‧‧基台 101‧‧‧Abutment

101a‧‧‧收納部 101a‧‧‧Storage Department

101b‧‧‧熔接面 101b‧‧‧welding joint

102‧‧‧蓋構件 102‧‧‧Caps

103‧‧‧電子零件 103‧‧‧Electronic parts

104‧‧‧凸塊 104‧‧‧Bumps

120‧‧‧焊料(銀焊料) 120‧‧‧Solder (silver solder)

圖1係本發明一實施形態的密封環平面圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a seal ring according to an embodiment of the present invention.

圖2係沿圖1中之300-300線的密封環構造剖視圖。 Figure 2 is a cross-sectional view of the seal ring taken along line 300-300 of Figure 1.

圖3係本發明一實施形態的密封環或蓋材,放大其焊料表面附近區域周邊的放大剖視圖。 Fig. 3 is an enlarged cross-sectional view showing a seal ring or a cover member according to an embodiment of the present invention, which is enlarged in the vicinity of a region near the solder surface.

圖4係本發明一實施形態使用密封環的電子零件收納用包裝之剖視圖。 Fig. 4 is a cross-sectional view showing a package for electronic component storage using a seal ring according to an embodiment of the present invention.

圖5係本發明一實施形態的密封環經沖孔加工後,且施行滾筒研磨前的密封環剖視圖。 Fig. 5 is a cross-sectional view showing a seal ring before punching of a seal ring according to an embodiment of the present invention.

圖6係本發明一實施形態的密封環經滾筒研磨後、且施行濕式蝕刻前的密封環剖視圖。 Fig. 6 is a cross-sectional view showing a seal ring before the wet etching is performed on the seal ring of the embodiment of the present invention after barrel polishing.

圖7係本發明一實施形態的蓋材平面圖。 Fig. 7 is a plan view showing a cover member according to an embodiment of the present invention.

圖8係本發明一實施形態使用蓋材的電子零件收納用包裝之剖視圖。 Fig. 8 is a cross-sectional view showing a package for electronic component storage using a lid member according to an embodiment of the present invention.

以下,針對本發明的具體化實施形態,根據圖式進行說明。 Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

首先,參照圖1~圖3,針對本發明一實施形態由設有焊料20的基材10所構成之密封環1之構造進行說明。另外,密封環1係本發明「具焊料基材」之一例。 First, a structure of a seal ring 1 composed of a base material 10 provided with a solder 20 according to an embodiment of the present invention will be described with reference to Figs. 1 to 3 . Further, the seal ring 1 is an example of the "solder base material" of the present invention.

本發明一實施形態的密封環1,如圖1所示,俯視觀之形成長方形框狀(環狀)。又,密封環1係如圖2所示,包括有在上側(Z1側)所配置的基材10與在下側(Z2側)所配置的焊料20,密封環1的四角落(形成圖2中所示略四角形截面的4個角)形成R面狀。另外,基材10在Z方向的厚度t1係約100μm以上且約130μm 以下,焊料20在Z方向的厚度t2係約5μm以上且約30μm以下。 As shown in Fig. 1, the seal ring 1 according to the embodiment of the present invention has a rectangular frame shape (annular shape) in plan view. Further, as shown in FIG. 2, the seal ring 1 includes a base material 10 disposed on the upper side (Z1 side) and a solder 20 disposed on the lower side (Z2 side), and the four corners of the seal ring 1 (formed in FIG. 2) The four corners of the slightly quadrangular cross section shown are formed in an R-face shape. Further, the thickness t1 of the substrate 10 in the Z direction is about 100 μm or more and about 130 μm. Hereinafter, the thickness t2 of the solder 20 in the Z direction is about 5 μm or more and about 30 μm or less.

基材10係從密封環1的上面1a起朝基材10與焊料20的界面(朝向Z2方向),依序積層著主要由Ni構成的Ni層11、中間層12、及主要由Cu構成的Cu層13而形成。另外,中間層12係主要由:約30質量%的Ni、約17質量%的Co、以及Fe構成,具有低熱膨脹係數的Fe-Ni-Co合金構成。另外,Cu層13係本發明「應力緩和層」之一例。 The substrate 10 is formed from the upper surface 1a of the seal ring 1 toward the interface between the substrate 10 and the solder 20 (toward the Z2 direction), and a Ni layer 11 mainly composed of Ni, an intermediate layer 12, and mainly composed of Cu are sequentially laminated. The Cu layer 13 is formed. Further, the intermediate layer 12 is mainly composed of an Fe-Ni-Co alloy having a low thermal expansion coefficient and consisting of approximately 30% by mass of Ni, about 17% by mass of Co, and Fe. Further, the Cu layer 13 is an example of the "stress relaxation layer" of the present invention.

Ni層11係具有提升密封環1上面1a之耐蝕性的機能。中間層12係藉由具有低熱膨脹係數,而具有縮小與構成後述電子零件收納用包裝100之基台101的陶瓷間之熱膨脹差機能。Cu層13係具有柔軟性,具有吸收因中間層12與基台101間之熱膨脹差而造成的熱應力與應變之機能。又,Cu層13係藉由熱傳導性佳,有效率地傳導熔接(焊接)地方附近的熱,故亦具有抑制熔接地方附近之熱應力變大的機能。 The Ni layer 11 has a function of improving the corrosion resistance of the upper surface 1a of the seal ring 1. The intermediate layer 12 has a low thermal expansion coefficient and has a function of reducing thermal expansion between ceramics constituting the base 101 of the electronic component storage package 100 to be described later. The Cu layer 13 is flexible and has a function of absorbing thermal stress and strain due to a difference in thermal expansion between the intermediate layer 12 and the base 101. Further, since the Cu layer 13 is excellent in thermal conductivity and efficiently conducts heat in the vicinity of the welded (welded) portion, it also has a function of suppressing an increase in thermal stress in the vicinity of the welded portion.

焊料20係由主要含有Ag與Cu的焊料構成。另外,構成焊料20的元素係除Ag及Cu之外,尚亦可含有Sn、Al、Zn、Cd、Ni、P及Mn中之任1種以上。另外,除Ag及Cu之外尚含有Sn的焊料(銀焊料),因為可縮小焊料20的固相線,因而可降低焊接溫度。其中,當使用焊料20中含有Sn的焊料(銀焊料)時,為能抑制在形成後述覆蓋材時的接合時會有軋延較為困難情形,最好Sn含有約6質量%以下。 The solder 20 is composed of a solder mainly containing Ag and Cu. In addition to the Ag and the Cu, the element constituting the solder 20 may contain at least one of Sn, Al, Zn, Cd, Ni, P, and Mn. Further, a solder (silver solder) containing Sn in addition to Ag and Cu can reduce the soldering temperature because the solid phase line of the solder 20 can be reduced. In the case where the solder (silver solder) containing Sn in the solder 20 is used, it is difficult to suppress the rolling at the time of forming the cover material described later, and Sn is preferably contained in an amount of about 6% by mass or less.

再者,焊料20全體(後述表面附近區域21及內部區域22雙方的區域,參照圖3),依Ag含有質量相對於Ag與Cu合計的比率(即Ag/(Ag+Cu)),較大於Cu含有質量對Ag與Cu合計的 比率(即Cu/(Ag+Cu))狀態構成。即,構成Ag含有質量比率較大於0.5。另外,焊料20全體的Ag含有質量比率最好大約0.64以上。 又,構成焊料20的銀焊料較佳係焊料20全體中的Ag含有質量比率為0.85以下。其中,Ag含有質量比率佔全體中為0.95以上的金屬,一般係有如銀950、純Ag(銀1000),該等的熔點係約930℃以上。即,因熔點過高,導致銀950、純Ag不適用於以熔接為目的之焊料(銀焊料)。 In addition, the total amount of the solder 20 (refer to FIG. 3 in the region near the surface 21 and the inner region 22 to be described later) is larger than the ratio of the Ag-containing mass to the total of Ag and Cu (that is, Ag/(Ag+Cu)). Cu contains mass for Ag and Cu total The ratio (ie Cu/(Ag+Cu)) state is composed. That is, the composition Ag has a mass ratio larger than 0.5. Further, the mass ratio of Ag contained in the entire solder 20 is preferably about 0.64 or more. Moreover, it is preferable that the silver solder constituting the solder 20 has a mass ratio of Ag in the entire solder 20 of 0.85 or less. Among them, Ag contains a metal having a mass ratio of 0.95 or more in total, and is generally, for example, silver 950 or pure Ag (silver 1000), and these melting points are about 930 ° C or higher. That is, since the melting point is too high, the silver 950 and the pure Ag are not suitable for the solder (silver solder) for the purpose of welding.

焊料20係如圖3所示,包括有:由從焊料20表面20a與從焊料20表面20a起接近深度方向的附近區域二者構成的表面附近區域21、以及表面附近區域21以外的內部區域22。另外,焊料20表面20a係位於密封環1的下面(Z2側之面)1b、與密封環1側面1c中焊料20所在位置的下部(Z2側之部分),沿其表面20a全域形成表面附近區域21。 As shown in FIG. 3, the solder 20 includes a surface vicinity region 21 composed of both the surface 20a of the solder 20 and a vicinity of the surface 20a from the surface 20a of the solder 20, and an inner region 22 other than the region 21 near the surface. . Further, the surface 20a of the solder 20 is located on the lower surface (surface on the Z2 side) 1b of the seal ring 1 and the lower portion (portion on the Z2 side) of the position where the solder 20 is located in the side surface 1c of the seal ring 1, and the vicinity of the surface is formed along the entire surface 20a thereof. twenty one.

其中,本實施形態,藉由優先除去表面附近區域21的Cu,使表面附近區域21的焊料20形成為Ag含有質量相對於Ag與Cu合計的比率為0.95以上。即,焊料20在表面附近區域21的焊料20之Ag含有質量比率,較大於內部區域22的Ag含有質量比率(優先除去Cu前的焊料中之Ag含有質量比率)。又,表面附近區域21係從焊料20的表面20a朝深度方向形成至1.3μm以上的深度L。即,表面附近區域21係在密封環1的下面(Z2側的面)1b朝Z1方向(深度方向)形成至1.3μm以上的深度L,且在密封環1的側面1c朝Z方向正交的X方向、或Y方向(深度方向,參照圖1)形成至1.3μm以上的深度L。 In the present embodiment, by preferentially removing Cu in the vicinity of the surface 21, the solder 20 in the vicinity of the surface 21 is formed so that the ratio of the Ag-containing mass to the total of Ag and Cu is 0.95 or more. That is, the Ag of the solder 20 in the vicinity of the surface region 21 contains a mass ratio of Ag, and the Ag content of the internal region 22 contains a mass ratio (Ag content ratio in the solder before preferential removal of Cu). Further, the surface vicinity 21 is formed from the surface 20a of the solder 20 toward the depth direction to a depth L of 1.3 μm or more. In other words, the surface vicinity region 21 is formed on the lower surface (surface on the Z2 side) 1b of the seal ring 1 in the Z1 direction (depth direction) to a depth L of 1.3 μm or more, and is orthogonal to the Z direction on the side surface 1c of the seal ring 1. The X direction or the Y direction (depth direction, see FIG. 1) is formed to a depth L of 1.3 μm or more.

另外,表面附近區域21的深度L係越深則腐蝕抑制 效果越高,因而距焊料20的表面20a朝深度方向較佳大約1.5μm以上的深度、更佳大約2.0μm以上的深度。又,因為若欲使表面附近區域21朝深度方向變大,則會有Ag從焊料20的表面20a溶出導致焊料20薄化的可能性,以及若熔點較高的Ag增加達豐富表面附近區域21的深度L必要以上,則焊料20不易熔解,會有導致焊接接合出現不良情況的可能性,因而表面附近區域21的深度L較佳係從焊料20的表面20a朝深度方向大約4.0μm以下的深度。 In addition, the deeper the depth L of the region 21 near the surface, the corrosion inhibition The higher the effect, the depth from the surface 20a of the solder 20 is preferably about 1.5 μm or more in the depth direction, more preferably about 2.0 μm or more. Further, if the surface vicinity 21 is to be increased in the depth direction, there is a possibility that Ag is eluted from the surface 20a of the solder 20 to cause the solder 20 to be thinned, and if the melting point is increased, Ag is increased to the area near the rich surface. If the depth L is more than necessary, the solder 20 is not easily melted, and there is a possibility that the solder joint may be defective. Therefore, the depth L of the region 21 near the surface is preferably from the surface 20a of the solder 20 to a depth of about 4.0 μm or less in the depth direction. .

再者,密封環1係如圖2所示,由構成基材10的Ni層11、中間層12及Cu層13、以及焊料20,從上面1a起朝下面1b,在厚度方向(Z方向)依序積層狀態相互接合。即,密封環1係由4層覆蓋材構成。結果構成密封環1的各層相互牢固地接合,4層中之任一界面均可抑制層彼此間發生剝離情形,且可抑制腐蝕因子滲入界面。 Further, as shown in FIG. 2, the seal ring 1 is composed of the Ni layer 11, the intermediate layer 12, the Cu layer 13, and the solder 20 constituting the substrate 10 from the upper surface 1a toward the lower surface 1b in the thickness direction (Z direction). The sequentially stacked states are joined to each other. That is, the seal ring 1 is composed of four layers of covering materials. As a result, the layers constituting the seal ring 1 are firmly joined to each other, and any of the four layers can suppress the peeling of the layers from each other, and can suppress the penetration of the corrosion factor into the interface.

再者,如圖4所示,密封環1係依使用於電子零件收納用包裝100構成。具體而言,電子零件收納用包裝100係具備有:本實施形態的密封環1、在密封環1下方(Z2側)且接合於密封環1的基台101、以及在密封環1上方(Z1側)且接合於密封環1的蓋構件102。而,藉由密封環1與基台101相接合,且密封環1與蓋構件102相接合,使經由凸塊104安裝著水晶振動元件等電子零件103的收納部101a構成氣密狀態。 Further, as shown in FIG. 4, the seal ring 1 is configured to be used in the electronic component storage package 100. Specifically, the electronic component storage package 100 includes the seal ring 1 of the present embodiment, the base 101 that is joined to the seal ring 1 below the seal ring 1 (on the Z2 side), and the seal ring 1 (Z1). Side) and joined to the cover member 102 of the seal ring 1. When the seal ring 1 is joined to the base 101 and the seal ring 1 is joined to the cover member 102, the accommodating portion 101a in which the electronic component 103 such as the crystal resonator element is attached via the bump 104 is in an airtight state.

基台101係利用氧化鋁等陶瓷形成,且形成無蓋的箱狀。又,箱狀基台101係具備有:在基台101中央部形成的收納部101a、以及形成於基台101的框狀壁部上面且與密封環1接合的四角形框狀熔接面101b。又,密封環1與基台101的框狀熔接面101b, 係利用密封環1的熔融焊料20相接合。其中,為提升基台101的熔接面101b與焊料20間之密接性,亦可在基台101的熔接面101b設置由W層、Ni層及Au層依序積層的覆金屬層。 The base 101 is formed of a ceramic such as alumina, and is formed in a box shape without a cover. Further, the box-shaped base 101 includes a housing portion 101a formed at the center of the base 101, and a square frame-shaped welding surface 101b formed on the upper surface of the frame-shaped wall portion of the base 101 and joined to the seal ring 1. Further, the seal ring 1 and the frame-shaped welded surface 101b of the base 101, The molten solder 20 of the seal ring 1 is joined. In order to improve the adhesion between the welded surface 101b of the base 101 and the solder 20, a metallized layer in which the W layer, the Ni layer, and the Au layer are sequentially laminated may be provided on the welded surface 101b of the base 101.

蓋構件102係由Fe-Ni-Co合金形成的平板狀構件所構成。又,蓋構件102與密封環1的基材10上面1a係利用縫焊等而接合。其中,為提升蓋構件102與基材10上面1a間之密接性,亦可在蓋構件102至少接合於基材10上面1a的區域,依序設置由Ni層及Au層積層的鍍敷層。 The cover member 102 is composed of a flat member formed of an Fe-Ni-Co alloy. Moreover, the cover member 102 and the upper surface 1a of the base material 10 of the seal ring 1 are joined by seam welding or the like. In order to improve the adhesion between the lid member 102 and the upper surface 1a of the substrate 10, a plating layer in which a Ni layer and an Au layer are laminated may be sequentially provided in a region where the lid member 102 is bonded to at least the upper surface 1a of the substrate 10.

其次,參照圖2、圖3、圖5及圖6,針對本發明一實施形態的密封環1之製造程序進行說明。 Next, a manufacturing procedure of the seal ring 1 according to an embodiment of the present invention will be described with reference to Figs. 2, 3, 5 and 6.

首先,準備主要由Ni構成的Ni板、由Fe-Ni-Co合金構成的中間板、主要由Cu構成的Cu板(未圖示)、以及主要含有Ag與Cu的焊料(銀焊料)120。另外,在此時點(優先除去Cu之前)的焊料120並未形成表面附近區域21,焊料120全體的Ag含有質量比率呈略一定。又,焊料120中,Ag含有質量相對於Ag與Cu合計的比率(即Ag/(Ag+Cu)),亦可大於Cu含有質量相對於Ag與Cu合計的比率(即Cu/(Ag+Cu))。 First, a Ni plate mainly composed of Ni, an intermediate plate made of Fe-Ni-Co alloy, a Cu plate (not shown) mainly composed of Cu, and a solder (silver solder) 120 mainly containing Ag and Cu are prepared. In addition, the solder 120 in this point (before preferentially removing Cu) does not form the surface vicinity region 21, and the Ag-containing mass ratio of the entire solder 120 is slightly constant. Further, in the solder 120, the Ag contains a mass ratio with respect to the total of Ag and Cu (i.e., Ag/(Ag+Cu)), and may be larger than the ratio of the Cu-containing mass to the total of Ag and Cu (i.e., Cu/(Ag+Cu). )).

然後,將Ni板、中間板、Cu板及焊料120,依在厚度方向呈依序積層狀態接合。藉此,形成由Ni層11、中間層12、Cu層13及焊料120相接合的覆蓋材(參照圖5)。另外,該覆蓋材係基材10的厚度及焊料120的厚度,分別相較於完成品的密封環1之基材10厚度t1(約100μm以上且約130μm以下,參照圖2)、及焊料20厚度t2(約5μm以上且約30μm以下,參照圖2),形成僅稍微大出後述利用滾筒研磨及濕式蝕刻進行的除去份量而已。 Then, the Ni plate, the intermediate plate, the Cu plate, and the solder 120 are joined in a layered state in the thickness direction. Thereby, a covering material in which the Ni layer 11, the intermediate layer 12, the Cu layer 13, and the solder 120 are joined is formed (see FIG. 5). Further, the thickness of the cover material base material 10 and the thickness of the solder 120 are respectively smaller than the thickness t1 of the base material 10 of the seal ring 1 of the finished product (about 100 μm or more and about 130 μm or less, see FIG. 2), and the solder 20 The thickness t2 (about 5 μm or more and about 30 μm or less, see FIG. 2) is formed only slightly larger than the amount of removal by barrel polishing and wet etching which will be described later.

然後,使用未圖示沖壓機,將覆蓋材施行沖孔為四角形框狀(環狀)(沖孔加工)。此時,覆蓋材係從焊料120側(Z2側)沿厚度方向(Z方向)施行沖孔。藉此,如圖5所示形成經沖孔呈環狀的密封環201a。另外,密封環201a在施行沖孔時會形成呈銳角狀突出的微小突起1d。又,圖5及圖6所示係密封環其中一部分切剖並放大。 Then, the covering material was punched into a rectangular frame shape (annular shape) (punching processing) using a press machine not shown. At this time, the covering material is punched in the thickness direction (Z direction) from the solder 120 side (Z2 side). Thereby, a seal ring 201a having a ring-shaped punched hole is formed as shown in FIG. Further, the seal ring 201a forms a minute projection 1d that protrudes in an acute angle when punching is performed. Further, a part of the seal ring shown in Figs. 5 and 6 is cut and enlarged.

然後,為除去密封環201a所形成的微小突起1d,施行滾筒研磨。具體而言,將複數密封環201a、由陶瓷等構成的介質(研磨材)、由化學粉末等構成的組合物及水等,投入滾筒(未圖示)中。接著,將滾筒依既定速度旋轉既定時間。藉此,藉由使介質碰撞微小突起1d等,如圖6所示,形成經除去微小突起1d的密封環201b。此時,密封環201b的四角落形成R面狀。另一方面,因為形成密封環201b之焊料120的銀焊料係硬度較小,因而由介質的殘渣等構成的異物2會依埋藏於焊料120露出表面120a中之方式附著。另外,該滾筒研磨係在施行後述濕式蝕刻的步驟之前實施。又,滾筒研磨係本發明「使用研磨材的研磨」一例。 Then, in order to remove the minute projections 1d formed by the seal ring 201a, barrel polishing is performed. Specifically, a plurality of seal rings 201a, a medium (abrasive material) made of ceramics or the like, a composition composed of chemical powder or the like, water, and the like are put into a drum (not shown). Next, the drum is rotated at a predetermined speed for a predetermined time. Thereby, by causing the medium to collide with the minute projections 1d and the like, as shown in FIG. 6, the seal ring 201b from which the minute projections 1d are removed is formed. At this time, the four corners of the seal ring 201b are formed in an R-face shape. On the other hand, since the solder of the solder 120 forming the seal ring 201b has a small hardness, the foreign matter 2 composed of the residue of the medium or the like adheres to the exposed surface 120a of the solder 120. Further, the barrel polishing is performed before the step of performing the wet etching described later. Further, the barrel polishing is an example of the "grinding using a polishing material" in the present invention.

其中,本實施形態之製造方法係對密封環201b施行濕式蝕刻(酸洗)。具體而言,將複數密封環201b、與約10℃以上且約30℃以下的蝕刻液投入未圖示滾筒中。 In the manufacturing method of this embodiment, the sealing ring 201b is subjected to wet etching (pickling). Specifically, the plurality of seal rings 201b and an etching liquid of about 10 ° C or more and about 30 ° C or less are placed in a drum (not shown).

該濕式蝕刻所使用的蝕刻液係在由含過氧化氫的氧化劑、與水依既定比例混合的原液、或更進一步添加水而依既定比例稀釋原液的稀釋液中,添加由稀硫酸所形成強酸的溶液所構成。 上述氧化劑係具有使焊料120中所含之Ag與Cu氧化,分別成為氧化銀與氧化銅的機能。另外,依焊料120較容易除去、且基材10 不易被除去的方式,構成上述蝕刻液。 The etching solution used in the wet etching is formed by diluting sulfuric acid in a dilution liquid which is diluted with a predetermined ratio of a oxidizing agent containing hydrogen peroxide, a stock solution mixed with water in a predetermined ratio, or a further addition of water. It is composed of a solution of strong acid. The oxidizing agent has a function of oxidizing Ag and Cu contained in the solder 120 to become silver oxide and copper oxide, respectively. In addition, it is easier to remove according to the solder 120, and the substrate 10 The etching liquid is formed in such a manner that it is difficult to remove.

再者,上述由稀硫酸構成的強酸係硫酸濃度約未滿90質量%的硫酸水溶液。其中,較佳係依硫酸濃度成為蝕刻液全體之約0.5質量%以上且約1.0質量%以下濃度的方式,將稀硫酸添加於蝕刻液中。又,更佳係依硫酸濃度成為蝕刻液全體之約0.7質量%以上且約1.0質量%以下濃度的方式,將稀硫酸添加至蝕刻液。 在此,上述由稀硫酸構成的強酸係具有就利用上述氧化劑所含的過氧化氫而生成的焊料120之氧化物(氧化銀及氧化銅)中,優先除去氧化銅的機能。藉此,在焊料120的表面120a,氧化銅可較氧化銀被優先除去。結果從焊料120的表面及表面附近的表面附近區域21(參照圖3)中優先除去Cu。另外,稀硫酸係本發明「優先除銅劑」之一例。又,對上述蝕刻液,亦可更進一步混合含有醋酸或氨的氧化物除去劑,此種氧化物除去劑具有溶解焊料的氧化銀與氧化銅並除去的機能,可除去因上述氧化劑而生成的氧化銀,且可提高除去氧化銅的機能。 Further, the above-mentioned strong acid-based sulfuric acid aqueous solution composed of dilute sulfuric acid has a sulfuric acid aqueous solution concentration of less than about 90% by mass. In particular, it is preferable to add dilute sulfuric acid to the etching solution so that the sulfuric acid concentration is about 0.5% by mass or more and about 1.0% by mass or less of the entire etching liquid. Moreover, it is more preferable to add dilute sulfuric acid to the etching liquid so that the sulfuric acid concentration becomes a concentration of about 0.7% by mass or more and about 1.0% by mass or less of the entire etching liquid. Here, the strong acid composed of the dilute sulfuric acid has a function of preferentially removing copper oxide in the oxide (silver oxide and copper oxide) of the solder 120 which is formed by the hydrogen peroxide contained in the oxidizing agent. Thereby, on the surface 120a of the solder 120, copper oxide can be preferentially removed compared to silver oxide. As a result, Cu is preferentially removed from the surface of the solder 120 and the surface vicinity 21 (see FIG. 3) near the surface. Further, dilute sulfuric acid is an example of the "preferred copper removal agent" of the present invention. Further, an oxide removing agent containing acetic acid or ammonia may be further mixed with the etching liquid, and the oxide removing agent has a function of dissolving silver oxide and copper oxide which are dissolved in solder, and can be removed by the oxidizing agent. Silver oxide, and can improve the function of removing copper oxide.

然後,使滾筒依既定速度僅旋轉既定時間。利用該濕式蝕刻,焊料120被等向性除去,另一方面,基材10則幾乎不會被除去。結果如圖2所示,將在焊料20露出表面20a中所埋藏由介質殘渣等構成的異物2(參照圖6)予以除去。又,如圖3所示,Ag含有質量相對於Ag與Cu合計的比率為0.95以上的表面附近區域21,係從焊料20的表面20a及表面20a起朝深度方向形成至1.3μm以上的深度L。又,焊料20全體中的Ag含有質量比率為0.64以上。然後,藉由施行水洗等,將焊料20表面20a殘留的殘渣予以除去,而製得圖1及圖2所示密封環1。 Then, the drum is rotated for only a predetermined time at a predetermined speed. With this wet etching, the solder 120 is removed isotropically, and on the other hand, the substrate 10 is hardly removed. As a result, as shown in FIG. 2, foreign matter 2 (see FIG. 6) made of a medium residue or the like is buried in the exposed surface 20a of the solder 20. In addition, as shown in FIG. 3, the vicinity of the surface 21 in which the ratio of Ag to the total of Ag and Cu is 0.95 or more is formed in the depth direction from the surface 20a and the surface 20a of the solder 20 to a depth L of 1.3 μm or more. . Further, the Ag contained in the entire solder 20 has a mass ratio of 0.64 or more. Then, the residue remaining on the surface 20a of the solder 20 is removed by performing water washing or the like to obtain the seal ring 1 shown in Figs. 1 and 2 .

其次,參照圖3、圖7及圖8,針對本發明一實施形態使用焊料20的蓋材3之構造進行說明。另外,蓋材3係本發明「具焊料基材」一例。 Next, a structure of the lid member 3 using the solder 20 according to an embodiment of the present invention will be described with reference to FIGS. 3, 7, and 8. Moreover, the cover material 3 is an example of the "solder base material" of this invention.

本發明一實施形態的蓋材3係如圖7所示,俯視觀之形成四角形的平板狀。又,蓋材3係如圖8所示,與上述密封環1同樣,含有:配置於上側(Z1側)的基材10與配置於下側(Z2側)的焊料20,且構成基材10的Ni層11、中間層12及Cu層13、以及焊料20,係從上面3a起朝向下面3b依在厚度方向(Z方向)上依序積層的狀態相互接合。即,蓋材3係與上述密封環1同樣的由4層覆蓋材所構成。 As shown in Fig. 7, the lid member 3 according to the embodiment of the present invention has a square shape in a plan view. In addition, as shown in FIG. 8, the cover member 3 includes the base material 10 disposed on the upper side (Z1 side) and the solder 20 disposed on the lower side (Z2 side), and constitutes the base material 10, as in the case of the seal ring 1. The Ni layer 11, the intermediate layer 12, the Cu layer 13, and the solder 20 are bonded to each other in a state in which they are sequentially stacked in the thickness direction (Z direction) from the upper surface 3a toward the lower surface 3b. That is, the cover member 3 is composed of four layers of the cover material similarly to the above-described seal ring 1.

再者,蓋材3的焊料20係與密封環1的焊料20同樣,如圖3所示,藉由優先除去表面附近區域21的Cu,而使表面附近區域21形成焊料20的Ag含有質量比率成為0.95以上。又,藉由優先除去表面附近區域21的Cu,構成表面附近區域21的焊料20之Ag含有質量比率,較大於內部區域22的Ag含有質量比率狀態。 又,表面附近區域21係從焊料20的表面20a起朝深度方向形成至1.3μm以上的深度L處。另外,圖8中,相關蓋材3形成表面附近區域21及內部區域22係省略圖示。又,蓋材3的基材10及焊料20的其他構成係與密封環1相同,因而省略說明。 Further, the solder 20 of the lid member 3 is the same as the solder 20 of the seal ring 1, and as shown in FIG. 3, the Ag content ratio of the solder 20 is formed in the vicinity of the surface region 21 by preferentially removing Cu in the region 21 near the surface. Become 0.95 or more. Further, by preferentially removing Cu in the vicinity of the surface 21, the Ag containing the surface 20 in the vicinity of the surface 21 contains a mass ratio, and the Ag in the inner region 22 contains a mass ratio state. Further, the surface vicinity 21 is formed in the depth direction from the surface 20a of the solder 20 to a depth L of 1.3 μm or more. In addition, in FIG. 8, the area vicinity 21 and the internal area 22 of the surface material formation surface of the related cover material 3 are abbreviate|omitted. Moreover, since the base material 10 of the cover material 3 and the other structure of the solder 20 are the same as that of the seal ring 1, description is abbreviate|omitted.

再者,如圖8所示,蓋材3係構成使用於電子零件收納用包裝200的狀態。具體而言,電子零件收納用包裝200係具備有:本實施形態的蓋材3、以及在蓋材3的下方(Z2側)且接合於蓋材3的基台101。而,藉由蓋材3與基台101的接合,構成安裝有電子零件103的收納部101a成為氣密狀態。另外,蓋材3與基台 101的框狀熔接面101b,係利用蓋材3的熔融焊料20而接合(熔接)。另外,基台101的構成係與使用密封環1的電子零件收納用包裝100同樣,故不再贅述。 Furthermore, as shown in FIG. 8, the cover material 3 is in a state of being used for the electronic component storage package 200. Specifically, the electronic component storage package 200 includes the cover member 3 of the present embodiment and a base 101 that is joined to the cover member 3 below the cover member 3 (on the Z2 side). By the joining of the lid member 3 and the base 101, the accommodating portion 101a on which the electronic component 103 is mounted is in an airtight state. In addition, the cover material 3 and the abutment The frame-shaped welded surface 101b of 101 is joined (welded) by the molten solder 20 of the lid member 3. The configuration of the base 101 is the same as that of the electronic component storage package 100 using the seal ring 1, and therefore will not be described again.

再者,本實施形態的蓋材3之製造程序,係除在沖孔加工時將覆蓋材沖孔為四角形平板狀之外,其餘均與上述密封環1之製造程序相同,故省略說明。 Further, the manufacturing procedure of the lid member 3 of the present embodiment is the same as the manufacturing procedure of the seal ring 1 except that the covering material is punched into a square-shaped flat plate at the time of punching, and thus the description thereof is omitted.

本實施形態可獲得如下述效果。 In the present embodiment, the following effects can be obtained.

本實施形態如上述,在表面附近區域21,藉由將焊料20的Ag含有質量相對於Ag與Cu合計的比率設定為0.95以上,而使涵蓋容易與外部腐蝕因子產生反應的焊料20表面20a在內之表面附近區域21,增加較Cu更低離子化傾向且耐蝕性較高的Ag含有質量比率,因而相反的可充分降低較Ag更高離子化傾向且耐蝕性較低的Cu含有質量比率,結果可充分抑制外部腐蝕因子(空氣中的氧、水分、以及氯化物離子等陰離子等)與Cu,於涵蓋焊料20表面20a在內的表面附近區域21產生反應情形。又,藉由表面附近區域21係從焊料20的表面20a朝深度方向形成至1.3μm以上的深度L,形成從焊料20的表面20a起至充分深度L處均不易受外部腐蝕因子影響狀態,因而可抑制外部腐蝕因子與Cu,於涵蓋焊料20表面20a在內的表面附近區域21產生反應。藉由該等,可抑制在焊料20的表面附近區域21生成腐蝕生成物。結果,可抑制因腐蝕生成物所造成的變色,而導致密封環1(蓋材3)的外觀感覺變差,且可抑制接著部混雜有腐蝕生成物,所以不僅可抑制因接著不良造成滲漏不良率情形增加,亦可抑制因腐蝕生成物造成的凹凸生成,故可抑制密封環1(蓋材3)的密封性降低。 In the present embodiment, as described above, by setting the ratio of the Ag-containing mass of the solder 20 to the total of Ag and Cu to 0.95 or more in the vicinity of the surface region 21, the surface 20a of the solder 20 which is likely to react with the external corrosion factor is covered. In the region 21 near the surface, the Ag having a lower ionization tendency than Cu and having a higher corrosion resistance has a mass ratio, and thus the Cu content having a higher ionization tendency and a lower corrosion resistance than Ag can be sufficiently reduced. As a result, external corrosion factors (anions such as oxygen, moisture, and chloride ions in the air) and Cu can be sufficiently suppressed to react in the region 21 near the surface covering the surface 20a of the solder 20. Further, since the surface vicinity 21 is formed from the surface 20a of the solder 20 toward the depth direction to a depth L of 1.3 μm or more, it is formed from the surface 20a of the solder 20 to a sufficient depth L to be less susceptible to external corrosion factors. The external corrosion factor and Cu can be suppressed from reacting in the region 21 near the surface covering the surface 20a of the solder 20. By this, it is possible to suppress generation of a corrosion product in the region 21 near the surface of the solder 20. As a result, discoloration due to the corrosion product can be suppressed, and the appearance of the seal ring 1 (the cover member 3) is deteriorated, and the corrosion product can be suppressed from being mixed in the joint portion, so that leakage due to poor adhesion can be suppressed. When the defect rate is increased, the generation of irregularities due to the corrosion product can be suppressed, so that the sealing property of the seal ring 1 (the cover member 3) can be suppressed from being lowered.

再者,本實施形態係在焊料20的表面附近區域21以外之內部區域22,不需要將Ag含有質量比率設定為0.95以上,因而可抑制焊料20本身的Ag含有量,結果可抑制焊料20的熔點提高,且可降低屬於貴金屬的Ag使用量。 Further, in the present embodiment, the internal region 22 other than the surface 21 in the vicinity of the surface of the solder 20 does not need to have the Ag content ratio of 0.95 or more, so that the Ag content of the solder 20 itself can be suppressed, and as a result, the solder 20 can be suppressed. The melting point is increased and the amount of Ag used in the precious metal can be reduced.

再者,本實施形態係就焊料20全體(表面附近區域21及內部區域22等二個區域),藉由將Ag含有質量比率設為大於Cu含有質量比率,優先除去焊料20表面附近區域21的Cu,當將表面附近區域21的Ag含有質量比率設定為0.95以上時,藉由將優先除去Cu前的焊料120之Ag含有質量比率較大於Cu含有質量比率,而可輕易地將焊料20的表面附近區域21之Ag含有質量比率形成為0.95以上。 In the present embodiment, the entire solder (the two regions such as the surface vicinity region 21 and the inner region 22) are preferentially removed from the vicinity of the surface of the solder 20 by setting the Ag-containing mass ratio to be larger than the Cu-containing mass ratio. When the Ag-containing mass ratio of the region 21 in the vicinity of the surface is set to 0.95 or more, the surface of the solder 20 can be easily removed by making the Ag-containing mass ratio of the solder 120 before preferentially removing Cu larger than the Cu-containing mass ratio. The Ag-containing mass ratio in the vicinity region 21 is formed to be 0.95 or more.

再者,本實施形態中,藉由將焊料20全體的Ag含有質量比率設定為0.64以上,優先除去焊料20表面附近區域21的Cu,當將表面附近區域21的Ag含有質量比率設定為0.95以上時,可更輕易地使焊料20表面附近區域21的Ag含有質量比率為0.95以上。 In the present embodiment, by setting the Ag-containing mass ratio of the entire solder 20 to 0.64 or more, Cu in the region 21 near the surface of the solder 20 is preferentially removed, and the Ag content ratio in the vicinity of the surface region 21 is set to 0.95 or more. In this case, the Ag-containing mass ratio of the region 21 in the vicinity of the surface of the solder 20 can be more easily made 0.95 or more.

再者,本實施形態中,藉由將焊料20全體的Ag含有質量比率設定為0.85以下,可抑制焊料20全體的Ag含有質量比率過度提高,所以可抑制焊料20全體的熔點過度提高。藉此,可抑制焊接溫度提高。 In addition, in the present embodiment, by setting the Ag-containing mass ratio of the entire solder 20 to 0.85 or less, it is possible to suppress an excessive increase in the Ag-containing mass ratio of the entire solder 20, and it is possible to suppress an excessive increase in the melting point of the entire solder 20. Thereby, the soldering temperature can be suppressed from increasing.

再者,本實施形態中,由構成基材10的Ni層11、中間層12及Cu層13、以及焊料20,從上面1a(3a)朝向下面1b(3b),依在厚度方向(Z方向)依序積層狀態進行接合的4層覆蓋材,構成密封環1(蓋材3)。藉此,可抑制在基材10與焊料20的界面處滲入 腐蝕因子,因而不僅焊料20的表面20a,基材10與焊料20的界面處均可抑制腐蝕生成物生成。結果,可抑制基材10與焊料20出現分離情形。結果,可更加提升具焊料基材(密封環1及蓋材3)的可靠度。 Further, in the present embodiment, the Ni layer 11, the intermediate layer 12, the Cu layer 13, and the solder 20 constituting the substrate 10 are oriented in the thickness direction from the upper surface 1a (3a) toward the lower surface 1b (3b). The four-layer cover material joined in the sequential build-up state constitutes the seal ring 1 (the cover member 3). Thereby, penetration at the interface between the substrate 10 and the solder 20 can be suppressed. The corrosion factor can suppress the generation of corrosion products not only at the surface 20a of the solder 20 but also at the interface between the substrate 10 and the solder 20. As a result, it is possible to suppress the separation of the substrate 10 from the solder 20. As a result, the reliability of the solder substrate (the sealing ring 1 and the cover material 3) can be further improved.

再者,本實施形態中,當作電子零件收納用包裝100的密封環1、或電子零件收納用包裝200的蓋材3使用之具焊料基材,藉由Ag含有質量比率為0.95以上的表面附近區域21係從焊料20的表面20a朝深度方向形成至1.3μm以上的深度,而可抑制在密封環1或蓋材3的焊料20之表面附近區域21生成腐蝕生成物情形。 In the present embodiment, the solder substrate used as the sealing ring 1 of the electronic component storage package 100 or the cover member 3 of the electronic component storage package 200 has a surface having a mass ratio of 0.95 or more. The vicinity region 21 is formed from the surface 20a of the solder 20 toward the depth direction to a depth of 1.3 μm or more, and it is possible to suppress the occurrence of a corrosion product in the region 21 near the surface of the solder 20 of the seal ring 1 or the cover member 3.

再者,本實施形態中,當焊料20係含有Ag、Cu及Sn的情況,將焊料20中的Sn含有率設定為6質量%以下。藉此,藉由焊料20中所含有的Sn,而可輕易地抑制焊接溫度提高。又,藉由將焊料20的Sn含有率設定在6質量%以下,而可抑制當製作密封環1或蓋材3時的加工性降低情形。特別係當將基材10與焊料20進行接合而製作覆蓋材時,可抑制軋延趨於困難情形。 In the present embodiment, when the solder 20 contains Ag, Cu, and Sn, the Sn content in the solder 20 is set to 6% by mass or less. Thereby, the increase in the soldering temperature can be easily suppressed by the Sn contained in the solder 20. In addition, by setting the Sn content of the solder 20 to 6 mass% or less, it is possible to suppress a decrease in workability when the seal ring 1 or the lid member 3 is produced. In particular, when the substrate 10 and the solder 20 are joined to each other to form a cover material, it is possible to suppress the rolling from becoming difficult.

再者,本實施形態中,藉由表面附近區域21係沿焊料20的表面20a全域形成,便可沿焊料20的表面20a全域抑制腐蝕生成物生成。 Further, in the present embodiment, by forming the entire surface 21 of the surface along the surface 20a of the solder 20, it is possible to suppress the generation of corrosion products along the entire surface 20a of the solder 20.

再者,本實施形態中,將表面附近區域21從焊料20的表面20a朝深度方向形成至1.5μm以上的深度L。又,較佳將表面附近區域21從焊料20的表面20a朝深度方向形成至2.0μm以上的深度L。藉由該等,可使從焊料20的表面20a起至更充分深度L處均呈不易受外部腐蝕因子影響的狀態,因而能有效地抑制外部腐 蝕因子與Cu在焊料20的表面附近區域21處產生反應。藉此可有效地抑制在焊料20的表面附近區域21處生成腐蝕生成物。 Further, in the present embodiment, the surface vicinity region 21 is formed from the surface 20a of the solder 20 toward the depth direction to a depth L of 1.5 μm or more. Further, it is preferable that the surface vicinity region 21 is formed from the surface 20a of the solder 20 toward the depth direction to a depth L of 2.0 μm or more. With these, it is possible to make the state from the surface 20a of the solder 20 to a more sufficient depth L which is less susceptible to external corrosion factors, thereby effectively suppressing external rot. The etch factor reacts with Cu at a region 21 near the surface of the solder 20. Thereby, generation of corrosion products at the region 21 near the surface of the solder 20 can be effectively suppressed.

再者,本實施形態中,表面附近區域21係從焊料20的表面20a朝深度方向形成至4.0μm以下的深度L。藉此,提高Ag含有質量比率,結果可抑制熔點較高的表面附近區域21之深度L過度增加,所以可抑制焊料20全體的熔點過度提高。藉此,可抑制焊接溫度提高。 Further, in the present embodiment, the surface vicinity region 21 is formed from the surface 20a of the solder 20 in the depth direction to a depth L of 4.0 μm or less. As a result, the Ag-containing mass ratio is increased, and as a result, the depth L of the region 21 near the surface having a high melting point can be suppressed from excessively increasing, so that the melting point of the entire solder 20 can be suppressed from being excessively increased. Thereby, the soldering temperature can be suppressed from increasing.

再者,本實施形態中,藉由在基材10的焊料20側形成主要由Cu構成的Cu層13,可利用具柔軟性之主要由Cu構成的Cu層13,吸收因焊料20與基材10間之熱膨脹差而造成的熱應力與應變,所以可抑制在熔接地方(焊接)附近發生剝離等情形。又,藉由Cu層13含有Cu,可提升Cu層13的熱傳導性,因而能有效地傳導熔接地方附近的熱。藉此可抑制熔接地方附近的熱應力變大。 Further, in the present embodiment, by forming the Cu layer 13 mainly composed of Cu on the side of the solder 20 of the substrate 10, the Cu layer 13 mainly composed of Cu having flexibility can be used to absorb the solder 20 and the substrate. The thermal stress and strain caused by the difference in thermal expansion between the 10 layers can suppress the occurrence of peeling in the vicinity of the welded portion (welding). Further, since the Cu layer 13 contains Cu, the thermal conductivity of the Cu layer 13 can be improved, so that heat in the vicinity of the welded portion can be efficiently conducted. Thereby, it is possible to suppress an increase in thermal stress near the welded portion.

再者,本實施形態之製造方法中,於濕式蝕刻時,藉由利用蝕刻液的過氧化氫水及硫酸,優先除去焊料20的表面附近區域21處之Cu,而被除去的Cu份量可輕易地使焊料20的表面附近區域21處之Ag含有質量比率增加。 Further, in the production method of the present embodiment, in the wet etching, Cu in the region 21 near the surface of the solder 20 is preferentially removed by hydrogen peroxide water and sulfuric acid in the etching solution, and the amount of Cu removed can be removed. The Ag-containing mass ratio at the region 21 near the surface of the solder 20 is easily increased.

再者,本實施形態之製造方法中,藉由優先除銅劑係添加屬於強酸的稀硫酸,可使離子化傾向較高的Cu之氧化物輕易地溶解於強酸中,另一方面,使離子化傾向較低的Ag之氧化物不易溶解於強酸中,因而可確實地優先除去Cu。又,生成屬於硫酸之陰離子的硫酸陰離子、與Cu陽離子的化合物(硫酸銅),所生成的化合物係呈水溶性,即可溶於蝕刻液中,因而藉由屬於強酸的硫 酸,可使焊料120的表面120a與表面附近區域21的Cu之氧化物,利用強酸而溶解,並在蝕刻液內析出Cu的氧化物,而可抑制附著於密封環1(蓋材3)。藉此,因為沒有必要設置從密封環1(蓋材3)除去所附著析出物的步驟,因而可形成簡單的密封環1(蓋材3)之製造步驟。 Further, in the production method of the present embodiment, by adding a dilute sulfuric acid which is a strong acid to the copper removal-preferring agent, the oxide of Cu having a high ionization tendency can be easily dissolved in the strong acid, and on the other hand, the ion is made. The oxide of Ag which has a low tendency to be dissolved is not easily dissolved in a strong acid, so that Cu can be surely removed preferentially. Further, a sulfuric acid anion belonging to an anion of sulfuric acid and a compound (copper sulfate) having a Cu cation are formed, and the resulting compound is water-soluble and can be dissolved in an etching solution, thereby being sulfur-containing a strong acid. The acid can dissolve the oxide of Cu on the surface 120a of the solder 120 and the Cu in the region 21 near the surface by a strong acid, and deposits Cu oxide in the etching liquid, thereby suppressing adhesion to the seal ring 1 (the lid member 3). Thereby, since it is not necessary to provide the step of removing the deposited precipitate from the seal ring 1 (the cover member 3), the manufacturing step of the simple seal ring 1 (the cover member 3) can be formed.

再者,本實施形態之製造方法中,在施行濕式蝕刻的步驟之前,較佳係施行例如滾筒研磨等利用研磨材施行研磨。藉此,例如利用沖孔等機械加工而形成的具焊料基材,因為利用濕式蝕刻無法輕易除去的毛邊、異物等可預先被除去,因而只要在濕式蝕刻中,調整焊料20的表面附近區域21成為能獲得本發明作用效果之既定狀態的處理條件即可,結果可使密封環1(蓋材3)之製造步驟簡單化。 Further, in the production method of the present embodiment, it is preferable to perform polishing using a polishing material such as barrel polishing before performing the step of wet etching. Thereby, for example, a solder substrate formed by machining such as punching can be removed in advance because burrs, foreign matter, and the like which cannot be easily removed by wet etching can be removed in advance, so that the surface of the solder 20 is adjusted in the wet etching. The region 21 may be a processing condition in which a predetermined state of action of the present invention can be obtained, and as a result, the manufacturing steps of the seal ring 1 (the lid member 3) can be simplified.

[實施例] [Examples]

其次,參照圖3、表1~表4,針對為確認本發明效果,而施行的密封環及蓋材之確認實驗(表面組成分析、表面附近區域的深度測定及耐蝕性試驗)進行說明。 Next, the confirmation test (surface composition analysis, depth measurement in the vicinity of the surface, and corrosion resistance test) of the seal ring and the lid member to be performed to confirm the effects of the present invention will be described with reference to FIG. 3 and Tables 1 to 4.

首先,製作確認實驗所使用的試驗材。具體而言,與上述實施形態同樣地,準備由Ni層11、中間層12、Cu層13及焊料120(Cu被優先除去前的焊料,參照圖5)接合的覆蓋材。此時,Cu被優先除去前的焊料係使用含有Ag:85質量%、其他含有Cu及微量元素的85Ag-Cu合金焊料(銀焊料)。然後,藉由使用未圖示沖壓機將覆蓋材沖孔呈環狀,而形成密封環201a(參照圖5)。然後,與上述實施形態同樣的對密封環201a施行滾筒研磨。 First, a test material used in the confirmation experiment was produced. Specifically, in the same manner as in the above embodiment, a covering material in which the Ni layer 11, the intermediate layer 12, the Cu layer 13, and the solder 120 (the solder before Cu is preferentially removed, see FIG. 5) is prepared. In this case, a solder containing Ag: 85% by mass and other 85Ag-Cu alloy solder (silver solder) containing Cu and trace elements was used as the solder before Cu was preferentially removed. Then, the cover ring is punched in a ring shape by using a press machine (not shown) to form a seal ring 201a (see FIG. 5). Then, the seal ring 201a is subjected to barrel polishing in the same manner as in the above embodiment.

其中,實施例1係對密封環201b(參照圖6)施行濕式 蝕刻(酸洗)。此時,蝕刻液係準備:由含醋酸25質量%的醋酸水、含過氧化氫35質量%的過氧化氫水、以及水,依1:5:4體積比進行混合的原液。然後,經在原液與水的體積比成為1:1之1:1稀釋液中,添加屬於強酸的稀硫酸者,使用為蝕刻液。此時,硫酸的濃度係調整成為佔蝕刻液全體的0.7質量%。然後,在25℃溫度條件下,將複數密封環與蝕刻液投入滾筒中,使滾筒依既定速度旋轉20分鐘後,施行水洗等。即,實施例1係施行20分鐘的濕式蝕刻。 藉此獲得實施例1的密封環。 Wherein, the first embodiment applies a wet type to the seal ring 201b (refer to FIG. 6). Etching (pickling). At this time, the etching liquid was prepared by mixing a raw liquid containing 25% by mass of acetic acid water containing acetic acid, 35% by mass of hydrogen peroxide containing hydrogen peroxide, and water at a volume ratio of 1:5:4. Then, a dilute sulfuric acid belonging to a strong acid is added to a 1:1 dilution solution in which the volume ratio of the stock solution to water is 1:1, and it is used as an etching solution. At this time, the concentration of sulfuric acid was adjusted to be 0.7% by mass based on the entire etching liquid. Then, a plurality of sealing rings and an etching liquid were placed in a drum at a temperature of 25 ° C, and the drum was rotated at a predetermined speed for 20 minutes, and then washed with water or the like. That is, Example 1 was subjected to wet etching for 20 minutes. Thereby, the seal ring of Example 1 was obtained.

另一方面,比較例1係直接使用未施行濕式蝕刻的密封環。又,比較例2、3及4係使用除濕式蝕刻分別改為施行1分鐘、5分鐘、及10分鐘之外,其餘均與實施例1同樣地製作的密封環。 On the other hand, in Comparative Example 1, a seal ring which was not subjected to wet etching was directly used. Further, in Comparative Examples 2, 3, and 4, a seal ring produced in the same manner as in Example 1 except that the dehumidification etching was performed for 1 minute, 5 minutes, and 10 minutes, respectively.

再者,在密封環之外,優先除去Cu前之焊料係使用85Ag-Cu合金焊料(銀焊料)的上述覆蓋材,藉由使用沖壓機沖孔呈平板狀,而形成蓋材。然後,對蓋材施行滾筒研磨。然後,實施例2係依照與實施例1同樣的條件施行濕式蝕刻(酸洗)。即,實施例2係施行20分鐘的濕式蝕刻。藉此獲得實施例2的蓋材。 Further, in addition to the seal ring, the solder before the Cu removal is preferentially used, and the cover material using 85Ag-Cu alloy solder (silver solder) is formed into a flat shape by punching using a press machine to form a cover material. Then, the cover material is subjected to barrel grinding. Then, in Example 2, wet etching (pickling) was carried out in the same manner as in Example 1. That is, Example 2 was subjected to wet etching for 20 minutes. Thereby, the cover material of Example 2 was obtained.

另一方面,比較例5係直接使用未施行濕式蝕刻的蓋材。又,比較例6、7及8係使用除濕式蝕刻分別改為施行1分鐘、5分鐘、及10分鐘之外,其餘均與實施例2同樣地製作的蓋材。 On the other hand, in Comparative Example 5, a lid member which was not subjected to wet etching was directly used. Further, in Comparative Examples 6, 7, and 8, a lid member produced in the same manner as in Example 2 except that the dehumidification etching was performed for 1 minute, 5 minutes, and 10 minutes, respectively.

再者,準備除優先除去Cu前之焊料係使用含Ag:72質量%之外,尚含有Cu及微量元素的72Ag-Cu合金焊料(銀焊料)之外,其餘均與實施例2同樣的覆蓋材。然後,使用未圖示沖壓機藉由將覆蓋材沖孔為平板狀,而形成蓋材。然後,對蓋材施行滾筒 研磨。 In addition, the solder before the Cu removal was preferentially used, except that the 72Ag-Cu alloy solder (silver solder) containing Cu and trace elements other than 72% by mass of Ag was used, and the same coverage as in Example 2 was carried out. material. Then, a cover material is formed by punching a cover material into a flat shape by using a press machine not shown. Then, applying a roller to the cover material Grinding.

然後,實施例3係使用除施行10分鐘的濕式蝕刻(酸洗)之外,其餘均依照與實施例2的濕式蝕刻為同樣條件施行濕式蝕刻,而製作的蓋材。又,實施例4係使用依照與實施例2同樣條件施行濕式蝕刻而製作的蓋材。即,實施例4係施行20分鐘的濕式蝕刻。 Then, in Example 3, a cover material produced by wet etching in the same manner as in the wet etching of Example 2 except that wet etching (pickling) was performed for 10 minutes was used. Further, in Example 4, a lid member produced by performing wet etching under the same conditions as in Example 2 was used. That is, Example 4 was subjected to wet etching for 20 minutes.

另一方面,比較例9係直接使用未施行濕式蝕刻的蓋材。又,比較例10及11係使用除濕式蝕刻分別改為施行1分鐘及5分鐘之外,其餘均與實施例3及4同樣地製作的蓋材。 On the other hand, in Comparative Example 9, a lid member which was not subjected to wet etching was directly used. Further, in Comparative Examples 10 and 11, a lid member produced in the same manner as in Examples 3 and 4 except that the dehumidification etching was performed for 1 minute and 5 minutes, respectively.

再者,準備除優先除去Cu前之焊料係使用含Ag:67質量%之外,尚含有Cu、若干Sn、及微量元素的67Ag-Cu-Sn合金焊料(銀焊料)之外,其餘均與實施例2同樣的覆蓋材。然後,使用未圖示沖壓機藉由將覆蓋材沖孔為平板狀,而形成蓋材。然後,對蓋材施行滾筒研磨。 In addition, the solder before the preferential removal of Cu is prepared using a 67Ag-Cu-Sn alloy solder (silver solder) containing Cu, some Sn, and a trace element, including Ag: 67% by mass. Example 2 was the same covering material. Then, a cover material is formed by punching a cover material into a flat shape by using a press machine not shown. Then, the cover material is subjected to barrel grinding.

再者,實施例5係使用除濕式蝕刻(酸洗)施行5分鐘之外,其餘均依照與實施例2的濕式蝕刻為同樣條件施行濕式蝕刻,而製作的蓋材。 Further, Example 5 was produced by wet etching under the same conditions as in the wet etching of Example 2, except that the wet etching (pickling) was performed for 5 minutes.

另一方面,比較例12係直接使用未施行濕式蝕刻的蓋材。又,比較例13係使用除濕式蝕刻分別改為施行1分鐘之外,其餘均與實施例5同樣地製作的蓋材。 On the other hand, in Comparative Example 12, a lid member which was not subjected to wet etching was directly used. Further, in Comparative Example 13, a lid member produced in the same manner as in Example 5 except that the dehumidification etching was performed for 1 minute was used.

然後,針對所製成的密封環及蓋材的焊料表面組成,使用電子探束微分析儀(Electron Probe MicroAnalyser:EPMA)進行觀察。又,將密封環及蓋材朝既定截面切剖後,使用掃描式電子顯微鏡-能量散佈式X射線分析裝置(SEM-EDX),觀察深度方向的Ag及Cu存 在量。然後,測量Ag含有質量比率為0.95以上的表面附近區域深度,距焊料表面朝深度方向的深度。 Then, the solder surface composition of the resulting seal ring and cover material was observed using an electron beam microanalyzer (EP). Further, after the seal ring and the lid member were cut into a predetermined cross section, the scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX) was used to observe the Ag and Cu in the depth direction. In quantity. Then, Ag was measured to have a depth in the vicinity of the surface having a mass ratio of 0.95 or more and a depth from the surface of the solder in the depth direction.

其次,施行耐蝕性試驗。該耐蝕性試驗係將上述實施例1與比較例1~4的密封環、以及實施例2~5與比較例5~13的蓋材,在85℃及85%Rh(相對濕度)恆溫恆濕條件下,施行放置470小時的恆溫恆濕試驗。然後,使用電子探束微分析儀觀察經恆溫恆濕試驗後的密封環及蓋材之焊料表面組成。又,藉由目視觀察經耐蝕性試驗後的實施例1與比較例1~4的密封環、以及實施例2~5與比較例5~13的蓋材之腐蝕程度,而針對密封環及蓋材的耐蝕性進行判斷。另外,表1~表4中,為求表格明確化,相關Ag含有質量相對於Ag與Cu合計的比率為0.95以上者、以及表面附近區域的深度為1.3μm以上者,利用實線粗框圈繞,而耐蝕性呈良好者的O(氧)質量%則利用虛線粗框圈繞。 Secondly, a corrosion resistance test was carried out. In the corrosion resistance test, the seal rings of the above-described Example 1 and Comparative Examples 1 to 4, and the cover materials of Examples 2 to 5 and Comparative Examples 5 to 13 were thermostated at 85 ° C and 85% Rh (relative humidity). Under the conditions, a constant temperature and humidity test was placed for 470 hours. Then, the solder surface composition of the seal ring and the cover material after the constant temperature and humidity test was observed using an electron beam microanalyzer. Moreover, the degree of corrosion of the seal ring of Example 1 and Comparative Examples 1 to 4 after the corrosion resistance test and the cover materials of Examples 2 to 5 and Comparative Examples 5 to 13 were visually observed for the seal ring and the cover. The corrosion resistance of the material is judged. In addition, in Tables 1 to 4, in order to clarify the table, the ratio of the Ag-containing mass to the total of Ag and Cu is 0.95 or more, and the depth in the vicinity of the surface is 1.3 μm or more. The O (oxygen) mass % which is wound and has good corrosion resistance is wound by a thick frame of a broken line.

表1係為確認本發明效果而施行具備85Ag-Cu合金焊料(銀焊料)的具焊料基材(密封環)之測定結果等之表格。 Table 1 is a table showing the results of measurement of a solder base material (sealing ring) including 85Ag-Cu alloy solder (silver solder) in order to confirm the effects of the present invention.

表2係為確認本發明效果而施行具備85Ag-Cu合金 焊料(銀焊料)的具焊料基材(蓋材)之測定結果等之表格。 Table 2 is an 85Ag-Cu alloy for confirming the effects of the present invention. A table of measurement results of solder (silver solder) having a solder substrate (cover material).

表3係為確認本發明效果而施行具備72Ag-Cu合金 焊料(銀焊料)的具焊料基材(蓋材)之測定結果等之表格。 Table 3 is for carrying out 72Ag-Cu alloy for confirming the effects of the present invention. A table of measurement results of solder (silver solder) having a solder substrate (cover material).

表4係為確認本發明效果而施行具備67Ag-Cu-Sn合金焊料(銀焊料)的具焊料基材(蓋材)之測定結果等之表格。 Table 4 is a table showing the results of measurement of a solder base material (cover material) having 67Ag-Cu-Sn alloy solder (silver solder) in order to confirm the effects of the present invention.

表1~表4所示實驗結果係從耐蝕試驗前的結果,藉由施行濕式蝕刻(酸洗),可確認到在焊料表面處,Ag含有質量相對於Ag與Cu合計的比率有增加。又,藉由至少施行1分鐘濕式蝕刻(實施例1~5、比較例2~4、6~8、10、11及13),焊料表面的Ag含有質量比率可增加至0.9以上,且藉由施行5分鐘以上濕式蝕刻(實施例1~5、比較例3、4、7、8及11),焊料表面的Ag含有質量比率可增加至0.95以上。藉此得知藉由施行5分鐘以上的濕式蝕刻,可使至少焊料表面的Ag含有質量比率為0.95以上,可形成本發明的表面附近區域。 The results shown in Tables 1 to 4 are from the results before the corrosion resistance test, and by performing wet etching (pickling), it was confirmed that the ratio of the Ag-containing mass to the total of Ag and Cu increased at the surface of the solder. Further, by performing at least one minute of wet etching (Examples 1 to 5, Comparative Examples 2 to 4, 6 to 8, 10, 11, and 13), the Ag content ratio of the solder surface can be increased to 0.9 or more, and By performing wet etching for 5 minutes or more (Examples 1 to 5, Comparative Examples 3, 4, 7, 8, and 11), the Ag content ratio on the surface of the solder can be increased to 0.95 or more. From this, it is understood that at least the mass ratio of Ag on the surface of the solder can be 0.95 or more by performing wet etching for 5 minutes or more, and the vicinity of the surface of the present invention can be formed.

另外,即便相較於由85Ag-Cu合金所構成之焊料,焊料全體中的Ag含有質量比率較低之焊料(72Ag-Cu合金及67Ag-Cu-Sn合金),藉由與85Ag-Cu合金同樣地施行達5分鐘以上 的濕式蝕刻(實施例3~5及比較例11),可使焊料表面的Ag含有質量比率增加至0.95以上。藉此,得知即便焊料全體的Ag含有質量比率較低的情況,藉由施行濕式蝕刻,可使焊料表面的Ag含有質量比率充分增加至0.95以上。另外,即便焊料全體的Ag含有質量比率未滿0.67的情況,但藉由施行適當的濕式蝕刻,判斷可使焊料表面的Ag含有質量比率充分增加至0.95以上。其中,為使焊料表面的Ag含有質量比率輕易地增加至0.95以上,而降低Cu除去量,因而在優先除去Cu前的焊料組成中,最好Ag含有質量比率較大於Cu含有質量比率。又,即便焊料全體的Ag含有質量比率設為0.64以上,判斷仍可輕易地使焊料表面的Ag含有質量比率增加至0.95以上。 In addition, even in the solder composed of the 85Ag-Cu alloy, Ag in the entire solder contains a solder having a low mass ratio (72Ag-Cu alloy and 67Ag-Cu-Sn alloy), and is the same as the 85Ag-Cu alloy. Execution for more than 5 minutes The wet etching (Examples 3 to 5 and Comparative Example 11) increased the Ag content ratio on the surface of the solder to 0.95 or more. As a result, even when the mass ratio of Ag in the entire solder is low, it is found that the Ag content ratio on the surface of the solder can be sufficiently increased to 0.95 or more by performing wet etching. In addition, even if Ag is contained in the entire solder, the mass ratio is less than 0.67. However, by performing appropriate wet etching, it is judged that the Ag content ratio on the solder surface can be sufficiently increased to 0.95 or more. In order to easily increase the Ag content ratio on the surface of the solder to 0.95 or more and reduce the Cu removal amount, it is preferable that the Ag content ratio is larger than the Cu content ratio in the solder composition before Cu is preferentially removed. In addition, even if the Ag content ratio of the entire solder is set to 0.64 or more, it is judged that the Ag content ratio on the solder surface can be easily increased to 0.95 or more.

再者,由耐蝕試驗後的結果,可確認到藉由施行濕式蝕刻(酸洗),當焊料的表面附近區域形成至較大於1.5μm深度的情況(實施例1~5),相較於未施行濕式蝕刻(酸洗)之情況下(比較例1、5、9及12),經耐蝕試驗後的焊料表面之氧量成為70%[=5.5(實施例2)/7.9(比較例5)×100(%)]以下。即,可確認到利用濕式蝕刻(酸洗),可充分降低焊料表面的氧量(質量%)。又,耐蝕性評價亦大略無法確認焊料表面的腐蝕(腐蝕生成物形成),可確認到耐蝕性良好。 Further, from the results of the corrosion resistance test, it was confirmed that by the wet etching (pickling), when the vicinity of the surface of the solder was formed to a depth of more than 1.5 μm (Examples 1 to 5), In the case where wet etching (pickling) was not performed (Comparative Examples 1, 5, 9 and 12), the amount of oxygen on the surface of the solder after the corrosion resistance test was 70% [= 5.5 (Example 2) / 7.9 (Comparative Example) 5) × 100 (%)] below. That is, it was confirmed that the amount of oxygen (% by mass) on the surface of the solder can be sufficiently reduced by wet etching (pickling). Further, in the evaluation of the corrosion resistance, corrosion of the solder surface (formation of corrosion products) was not confirmed, and it was confirmed that the corrosion resistance was good.

另一方面,當藉由施行濕式蝕刻而使焊料的表面附近區域形成至1.2μm以下深度的情況(比較例2~4、6~8、10、11及13),相較於未施行濕式蝕刻的情況(比較例1、5、9及12),可使耐蝕試驗後的焊料表面之氧量成為81%[=7.2(比較例3)/8.8(比較例1)×100(%)]以上。即,確認到依照濕式蝕刻(酸洗)的處理時間,可充分降低焊料表面的氧量。又,就耐蝕性評價,亦是除焊料表面附 近區域形成至1.2μm深度的情況(比較例11)外(比較例2~4、6~8、10及13),均在焊料表面確認有腐蝕(腐蝕生成物形成),確認到耐蝕性不佳。此現象可認為比較例2~4、6~8、10及13中,濕式蝕刻(酸洗)不足,導致焊料的表面附近區域無法形成至足夠深度的緣故所致。 On the other hand, when wet etching is performed to form a region near the surface of the solder to a depth of 1.2 μm or less (Comparative Examples 2 to 4, 6 to 8, 10, 11, and 13), wet is not performed. In the case of the etching (Comparative Examples 1, 5, 9, and 12), the amount of oxygen on the surface of the solder after the corrosion resistance test was 81% [= 7.2 (Comparative Example 3) / 8.8 (Comparative Example 1) × 100 (%) ]the above. That is, it was confirmed that the amount of oxygen on the surface of the solder can be sufficiently reduced in accordance with the processing time of the wet etching (pickling). Also, in terms of corrosion resistance, it is also attached to the solder surface. When the near region was formed to a depth of 1.2 μm (Comparative Example 11) (corresponding to Examples 2 to 4, 6 to 8, 10, and 13), corrosion was observed on the surface of the solder (corrosion product formation), and corrosion resistance was confirmed. good. This phenomenon is considered to be caused by insufficient wet etching (pickling) in Comparative Examples 2 to 4, 6 to 8, 10, and 13, and the region near the surface of the solder cannot be formed to a sufficient depth.

再者,焊料的表面附近區域形成至1.2μm深度的情況(比較例11),雖耐蝕試驗後的焊料表面腐蝕程度較小,但成為與沒有施行濕式蝕刻的情況(比較例9)為同樣氧量(3.7wt%),判斷耐蝕性不足。 Further, in the case where the vicinity of the surface of the solder was formed to a depth of 1.2 μm (Comparative Example 11), the degree of corrosion of the solder surface after the corrosion resistance test was small, but it was the same as in the case where wet etching was not performed (Comparative Example 9). The amount of oxygen (3.7 wt%) was judged to be insufficient in corrosion resistance.

由該等結果得知,藉由Ag含有質量比率為0.95以上的本發明表面附近區域,係從焊料表面朝深度方向形成至較1.2μm更深的1.3μm深度處,而可抑制焊料表面的腐蝕(腐蝕生成物形成),使耐蝕性呈良好。又,得知藉由Ag含有質量比率為0.95以上的本發明表面附近區域,係從焊料表面朝深度方向形成至1.5μm以上的深度,而可確實地抑制焊料表面的腐蝕(腐蝕生成物形成),可使耐蝕性呈良好。 From these results, it is known that the region near the surface of the present invention having Ag having a mass ratio of 0.95 or more is formed from the surface of the solder toward the depth direction to a depth of 1.3 μm deeper than 1.2 μm, thereby suppressing corrosion of the solder surface ( The corrosion product is formed to have good corrosion resistance. In addition, it is found that the region near the surface of the present invention having a mass ratio of 0.95 or more is formed to a depth of 1.5 μm or more from the surface of the solder, and the corrosion of the solder surface (corrosion product formation) can be reliably suppressed. It can make the corrosion resistance good.

另外,未施行濕式蝕刻(酸洗)的比較例1、5、9及12之Ag質量%(78.7、79.0、67.4及60.9),分別較小於所使用焊料的Ag質量%(85、85、72及67)之理由,可認為因覆蓋材形成時(接合時)與滾筒研磨等所生成的熱,導致在Ag-Cu(-Sn)合金內容易擴散的Cu,朝表面側進行擴散,而此部分相反的會導致Ag質量%降低的緣故所致。 Further, Ag mass% (78.7, 79.0, 67.4, and 60.9) of Comparative Examples 1, 5, 9, and 12 which were not subjected to wet etching (pickling) were smaller than Ag mass% of the solder used (85, 85, respectively). In the case of the formation of the cover material (at the time of joining) and the heat generated by the barrel polishing, it is considered that Cu which is easily diffused in the Ag-Cu (-Sn) alloy diffuses toward the surface side. The opposite of this part will result in a decrease in Ag mass%.

另外,本次所揭示的實施形態及實施例全部均僅止於例示而已,不應認為係屬限制。本發明的範圍並不僅侷限於上述實 施形態及實施例的說明,而是依照申請專利範圍所示,更涵蓋在與 申請專利範圍具均等涵義及範疇內之所有變更。 In addition, the embodiments and examples disclosed herein are merely illustrative, and should not be construed as limiting. The scope of the present invention is not limited to the above The description of the embodiment and the embodiment, but according to the scope of the patent application, is further covered in The scope of the patent application has the same meaning and all changes within the scope.

例如,上述本實施形態中,例示經滾筒研磨後再施行濕式蝕刻的例子,惟本發明並不僅侷限於此。本發明亦可未施行滾筒研磨。藉此,不需要滾筒研磨用的設備,可使製造步驟簡單化。 又,使用研磨材施行的研磨亦可施行滾筒研磨以外的研磨。 For example, in the above-described embodiment, an example in which wet etching is performed after barrel polishing is exemplified, but the present invention is not limited thereto. The present invention may also not perform barrel grinding. Thereby, the apparatus for barrel polishing is not required, and the manufacturing steps can be simplified. Further, the polishing by the polishing material may be performed by polishing other than the barrel polishing.

再者,上述實施形態係例示基材10由Ni層11、中間層12及Cu層13等3層構成的例子,惟本發明並不僅侷限於此。 本發明中,基材係可構成由單層(單一材料)構成,亦可構成由2層或4層以上的複數層形成。又,基材並不僅侷限於金屬,亦可由例如陶瓷、耐熱樹脂等構成。 In the above embodiment, the substrate 10 is exemplified by three layers of the Ni layer 11, the intermediate layer 12, and the Cu layer 13, but the present invention is not limited thereto. In the present invention, the substrate may be composed of a single layer (single material) or a plurality of layers of two or more layers. Further, the substrate is not limited to a metal, and may be composed of, for example, ceramics, a heat resistant resin, or the like.

再者,上述實施形態係例示密封環1(蓋材3)由基材10與焊料20相互接合的覆蓋材構成例,惟本發明並不僅侷限於此。本發明亦可使基材與焊料如覆蓋材般的未相接合。例如亦可將焊料塗佈於基材其中一表面。 In the above embodiment, the sealing ring 1 (the cover member 3) is exemplified by a covering material in which the base material 10 and the solder 20 are joined to each other, but the present invention is not limited thereto. The present invention also allows the substrate to be bonded to a solder such as a cover material. For example, solder may be applied to one of the surfaces of the substrate.

再者,上述實施形態中,就本發明的具焊料基材例係例示電子零件收納用包裝100及200分別使用的密封環1及蓋材3,惟本發明並不僅侷限於此。本發明中,除電子零件收納用包裝以外的用途所使用之具焊料基材,亦適用本發明的構成。例如熱交換器所使用的具焊料基材亦可適用本發明的構成。 In the above-described embodiment, the seal ring 1 and the lid member 3 which are used for the electronic component storage packages 100 and 200, respectively, are exemplified, and the present invention is not limited thereto. In the present invention, the configuration of the present invention is also applicable to a solder base material used for applications other than the electronic component storage package. For example, the structure of the present invention can also be applied to a solder substrate used in a heat exchanger.

再者,上述實施例,就優先除去Cu前的焊料係例示使用85Ag-Cu合金、72Ag-Cu合金、及67Ag-Cu-Sn合金的銀焊料(焊料)的例子,惟本發明並不僅侷限於此。本發明中,焊料亦可使用其他組成的焊料。 Further, in the above embodiment, the solder before the removal of Cu is exemplified as an example of a silver solder (solder) using an 85Ag-Cu alloy, a 72Ag-Cu alloy, and a 67Ag-Cu-Sn alloy, but the present invention is not limited to the invention. this. In the present invention, the solder may be solder of other compositions.

再者,上述實施形態中,優先除銅劑係例示含有由稀硫酸構成強酸的例子,惟本發明並不僅侷限於此。本發明亦可包括將例如鹽酸等除稀硫酸之外的強酸,使用為優先除銅劑。又,在能優先除去Cu的前提下,亦涵蓋將強酸以外的溶液(例如強鹼性溶液)使用為優先除銅劑。 Further, in the above embodiment, the preferred copper removal agent is exemplified as containing a strong acid composed of dilute sulfuric acid, but the present invention is not limited thereto. The present invention may also include a strong acid other than dilute sulfuric acid such as hydrochloric acid, which is used as a preferred copper removal agent. Further, in the case where Cu can be preferentially removed, a solution other than a strong acid (for example, a strongly alkaline solution) is preferably used as a preferred copper removal agent.

1‧‧‧密封環 1‧‧‧Seal ring

1a‧‧‧上面 1a‧‧‧above

1b(20a)‧‧‧表面 1b (20a) ‧ ‧ surface

1c‧‧‧側面 1c‧‧‧ side

10‧‧‧基材 10‧‧‧Substrate

11‧‧‧Ni層 11‧‧‧Ni layer

12‧‧‧中間層 12‧‧‧Intermediate

13‧‧‧Cu層 13‧‧‧Cu layer

20‧‧‧焊料 20‧‧‧ solder

21‧‧‧表面附近區域 21‧‧‧The area near the surface

22‧‧‧內部區域 22‧‧‧Internal area

t1、t2‧‧‧厚度 T1, t2‧‧‧ thickness

Z‧‧‧方向(厚度方向) Z‧‧‧ direction (thickness direction)

Z1‧‧‧上側 Z1‧‧‧ upper side

Z2‧‧‧下側 Z2‧‧‧ underside

Y‧‧‧方向(深度方向) Y‧‧‧ direction (depth direction)

Claims (19)

一種具焊料基材,係具備有:基材;以及形成於上述基材上,且至少含有Ag與Cu的焊料;上述焊料中,Ag含有質量相對於Ag與Cu合計的比率為0.95以上之表面附近區域,係形成於從上述焊料表面起朝深度方向至1.3μm以上且4.0μm以下之深度處;上述焊料在上述表面附近區域以外之內部區域的Ag含有質量比率係小於上述焊料在上述表面附近區域的Ag含有質量比率。 A solder base material comprising: a base material; and a solder formed on the base material and containing at least Ag and Cu; wherein the Ag contains a surface having a mass ratio of 0.95 or more with respect to a total of Ag and Cu The vicinity is formed in a depth direction from the surface of the solder to a depth of 1.3 μm or more and 4.0 μm or less; an Ag content ratio of the solder in an inner region other than the vicinity of the surface is smaller than the solder in the vicinity of the surface The Ag of the region contains a mass ratio. 如申請專利範圍第1項之具焊料基材,其中,上述焊料中,Ag含有質量相對於Ag與Cu合計的比率,係大於Cu含有質量相對於Ag與Cu合計的比率。 The solder substrate according to the first aspect of the invention, wherein the Ag contains a ratio of the mass of the Ag to the total of Ag and Cu, and is greater than a ratio of the Cu content to the total of Ag and Cu. 如申請專利範圍第1項之具焊料基材,其中,上述焊料全體中的Ag含有質量比率係0.64以上。 The solder base material according to the first aspect of the invention is characterized in that the Ag content in the entire solder contains a mass ratio of 0.64 or more. 如申請專利範圍第1項之具焊料基材,其中,上述焊料全體中的Ag含有質量比率係0.85以下。 A solder base material according to the first aspect of the invention, wherein the Ag content in the entire solder contains a mass ratio of 0.85 or less. 如申請專利範圍第1項之具焊料基材,其中,藉由上述基材與上述焊料相互接合而形成的覆蓋材所構成。 A solder base material according to claim 1, wherein the base material and the solder are bonded to each other to form a cover material. 如申請專利範圍第1項之具焊料基材,其中,作為電子零件收納用包裝的密封環使用。 A solder base material according to the first aspect of the patent application, which is used as a seal ring for an electronic component storage package. 如申請專利範圍第1項之具焊料基材,其中,作為電子零件收納用包裝的蓋材使用。 The solder base material of the first aspect of the patent application is used as a cover material for the electronic component storage package. 如申請專利範圍第1項之具焊料基材,其中,上述焊料係含有Ag、Cu及Sn; 上述焊料中的Sn含有率係6質量%以下。 1. The solder substrate of claim 1, wherein the solder contains Ag, Cu, and Sn; The Sn content in the solder is 6% by mass or less. 如申請專利範圍第1項之具焊料基材,其中,上述表面附近區域係沿上述焊料的表面全域形成。 A solder substrate according to the first aspect of the invention, wherein the region near the surface is formed along the entire surface of the solder. 如申請專利範圍第1項之具焊料基材,其中,上述表面附近區域係從上述焊料表面朝深度方向形成至1.5μm以上的深度處。 A solder substrate according to the first aspect of the invention, wherein the region in the vicinity of the surface is formed to a depth of 1.5 μm or more from the solder surface toward the depth direction. 如申請專利範圍第10項之具焊料基材,其中,上述表面附近區域係從上述焊料表面朝深度方向形成至2.0μm以上的深度處。 A solder substrate according to claim 10, wherein the region in the vicinity of the surface is formed in a depth direction from the solder surface to a depth of 2.0 μm or more. 如申請專利範圍第1項之具焊料基材,其中,在上述基材的上述焊料側形成含有Cu的應力緩和層。 A solder substrate according to the first aspect of the invention, wherein a stress relaxation layer containing Cu is formed on the solder side of the substrate. 一種具焊料基材之製造方法,係包括有:對基材上所形成至少含有Ag與Cu的焊料,使用含有用以優先除去Cu之優先除銅劑的蝕刻液,施行濕式蝕刻的步驟;其中,藉由在上述濕式蝕刻中,利用上述蝕刻液的優先除銅劑,優先除去上述焊料表面附近區域的Cu,使Ag含有質量相對於Ag與Cu合計的比率為0.95以上的表面附近區域,從上述焊料表面朝深度方向形成至1.3μm以上且4.0μm以下之深度處;將上述焊料在上述表面附近區域的Ag含有質量比率設為大於上述焊料在上述表面附近區域以外之內部區域的Ag含有質量比率。 A method for manufacturing a solder substrate, comprising: a step of performing wet etching using an etching solution containing at least Ag and Cu on a substrate, using an etching solution containing a preferential copper removing agent for preferentially removing Cu; In the above-described wet etching, Cu is preferentially removed by the preferential copper removal agent of the etching liquid, and Cu is preferentially removed, and the ratio of the Ag-containing mass to the total of Ag and Cu is 0.95 or more. The solder surface is formed in the depth direction to a depth of 1.3 μm or more and 4.0 μm or less; and the Ag-containing mass ratio of the solder in the vicinity of the surface is set to be larger than the Ag in the inner region other than the region near the surface of the solder. Contains mass ratio. 如申請專利範圍第13項之具焊料基材之製造方法,其中,上述優先除銅劑係含有強酸。 The method for producing a solder substrate according to claim 13, wherein the preferred copper removal agent contains a strong acid. 如申請專利範圍第14項之具焊料基材之製造方法,其中,上述優先除銅劑係含有屬於上述強酸的硫酸。 The method for producing a solder substrate according to claim 14, wherein the preferential copper removal agent contains sulfuric acid belonging to the strong acid. 如申請專利範圍第13項之具焊料基材之製造方法,其中,在施行上述濕式蝕刻的步驟之前,更進一步包括有使用研磨材施行研 磨的步驟。 The method for manufacturing a solder substrate according to claim 13 , wherein before the step of performing the wet etching, further comprising using the abrasive material The step of grinding. 如申請專利範圍第13項之具焊料基材之製造方法,其中,上述焊料中,Ag含有質量相對於Ag與Cu合計的比率,係較大於Cu含有質量相對於Ag與Cu合計的比率。 The method for producing a solder substrate according to the thirteenth aspect of the invention, wherein the ratio of the mass of Ag to the total of Ag and Cu is larger than the ratio of the mass of Cu to the total of Ag and Cu. 如申請專利範圍第13項之具焊料基材之製造方法,其中,上述焊料全體中的Ag含有質量比率係0.64以上。 The method for producing a solder substrate according to claim 13, wherein the Ag contains a mass ratio of 0.64 or more. 如申請專利範圍第13項之具焊料基材之製造方法,其中,在施行上述濕式蝕刻的步驟之前,更進一步包括有藉由使上述基材與上述焊料相互接合而形成覆蓋材的步驟。 The method for producing a solder substrate according to claim 13 , further comprising the step of forming a covering material by bonding the substrate and the solder to each other before the step of performing the wet etching.
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