TW201706421A - Au-Sn-Ag based solder paste, and electronic component joined or sealed by using Au-Sn-Ag based solder paste - Google Patents
Au-Sn-Ag based solder paste, and electronic component joined or sealed by using Au-Sn-Ag based solder paste Download PDFInfo
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- TW201706421A TW201706421A TW105112442A TW105112442A TW201706421A TW 201706421 A TW201706421 A TW 201706421A TW 105112442 A TW105112442 A TW 105112442A TW 105112442 A TW105112442 A TW 105112442A TW 201706421 A TW201706421 A TW 201706421A
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- mass
- alloy
- solder
- solder alloy
- solder paste
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/02—Containers; Seals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
本發明有關高溫用之無Pb銲膏。尤其有關適合作為高溫用之將以Au為主成分之Au-Sn-Ag系焊料合金與助焊劑混合而得之Au-Sn-Ag系焊膏及使用此焊膏接合或密封之電子元件。 The invention relates to a Pb-free solder paste for high temperature use. In particular, an Au-Sn-Ag-based solder paste which is suitable for high-temperature use of an Au-Sn-Ag-based solder alloy containing Au as a main component and a flux, and an electronic component bonded or sealed using the solder paste.
近幾年來，對於環境有害之化學物質之規範日益嚴苛。該規範對於將電子零件等接合於基板為目的而使用之焊料合金亦不例外。焊料合金中過去以來持續使用鉛為主成分，但也成為RoHS指令等之規範對象物質。因此，正盛行開發不含鉛(Pb)之焊料合金(以下稱為無Pb焊料合金或無鉛焊料合金)。 In recent years, the specifications for environmentally harmful chemicals have become increasingly stringent. This specification is no exception to the solder alloy used for bonding electronic parts and the like to a substrate. In the past, solder alloys have been used as a main component in the past, but they have become the subject of the RoHS directive. Therefore, a lead-free (Pb)-free solder alloy (hereinafter referred to as a Pb-free solder alloy or a lead-free solder alloy) is being actively developed.
將電子零件接合於基板時使用之焊料合金根據其使用臨界溫度大致分為高溫用(約260℃~400℃)與中低溫用(約140℃~230℃)。高溫用與中低溫用中，關於中低溫用焊料合金以Sn為主成分者之無鉛已實用化。 The solder alloy used for bonding the electronic component to the substrate is roughly classified into a high temperature (about 260 ° C to 400 ° C) and a medium low temperature (about 140 ° C to 230 ° C) depending on the critical temperature. In the case of high-temperature use and medium-low temperature use, lead-free has been put into practical use in the case of Sn as a main component of a solder alloy for medium and low temperature.
例如，專利文獻1中記載以Sn為主成分，含有Ag 1.0~4.0重量%，Cu 2.0重量%以下、Ni 1.0重量%以下之無鉛焊料合金組成。 For example, Patent Document 1 discloses that Sn is contained as a main component and contains Ag. 1.0 to 4.0% by weight, Cu 2.0% by weight or less, and Ni 1.0% by weight or less of a lead-free solder alloy composition.
又，專利文獻2中記載含有Ag 0.5~3.5重量%、Cu 0.5~2.0重量%，其餘部分由Sn所成之合金組成之無鉛焊料。 Further, Patent Document 2 describes a lead-free solder containing an alloy of 0.5 to 3.5% by weight of Ag and 0.5 to 2.0% by weight of Cu, and the balance being made of an alloy of Sn.
另一方面，關於高溫用無Pb焊料合金已由各種機構進行開發。例如專利文獻3中揭示氣密端子，其特徵係於焊接連接部成膜Bi組成比為30~80at%之非共晶Ag-Bi合金、及其組成比之Ag-Bi為主成分之Ag-Bi-α(其餘部分)合金。而且揭示對氣密端子之焊接連接部吹附350~500℃之熱風，使AgBi合金熔解而連接。 On the other hand, the Pb-free solder alloy for high temperature has been developed by various mechanisms. For example, Patent Document 3 discloses a hermetic terminal characterized in that a non-eutectic Ag-Bi alloy having a Bi composition ratio of 30 to 80 at% and a composition ratio of Ag-Bi as a main component of Ag-Bi are formed in a welded joint portion. Bi-α (the rest) alloy. Further, it is disclosed that hot air of 350 to 500 ° C is blown to the welded joint portion of the hermetic terminal, and the AgBi alloy is melted and connected.
且，專利文獻4中揭示於含有Bi之2元共晶合金所成之第1金屬成分中添加2元共晶合金的第2金屬成分，進而添加第3金屬成分，而使熔點成為250~300℃之焊料之生產方法。 Further, Patent Document 4 discloses that a second metal component in which a two-membered eutectic alloy is added to a first metal component containing a Bi-based eutectic alloy containing Bi, and a third metal component is further added, and a melting point of 250 to 300 is obtained. °C solder production method.
作為昂貴之高溫用無Pb焊料合金，Au-Sn合金或Au-Ge合金等以於石英裝置、SAW過濾器而且於MEMS等中使用。 As an expensive high-temperature Pb-free solder alloy, an Au-Sn alloy or an Au-Ge alloy is used in a quartz device, a SAW filter, and a MEMS or the like.
Au-20質量%Sn(意指由80質量%之Au與20質量%Sn構成，以下同)係共晶點之組成，其熔點為280℃。另一方面，Au-12.5質量%Ge為共晶點之組成，其熔點為356℃。 Au-20% by mass Sn (which is composed of 80% by mass of Au and 20% by mass of Sn, the same applies hereinafter) is a composition of a eutectic point, and its melting point is 280 °C. On the other hand, Au-12.5 mass% Ge is a composition of a eutectic point, and its melting point is 356 °C.
Au-Sn合金與Au-Ge合金之使用區分首先係根據其熔點差異。亦即，稱為高溫用而亦使用於溫度比較低 之部位之接合用時係使用Au-Sn合金。而且，於比較高溫之情況係使用Au-Ge合金。進而Au系焊料合金與Pb系焊料合金或Sn系焊料合金相比非常硬。尤其Au-Ge合金由於Ge為半金屬，故難以加工成薄片形狀等。因此，生產性或收率差，成為成本增加之原因。 The use of Au-Sn alloys and Au-Ge alloys is first distinguished by the difference in melting point. That is, it is called high temperature and is also used for lower temperature. The Au-Sn alloy is used for the joining of the parts. Moreover, an Au-Ge alloy is used in the case of a relatively high temperature. Further, the Au-based solder alloy is very hard compared to the Pb-based solder alloy or the Sn-based solder alloy. In particular, the Au-Ge alloy is difficult to process into a sheet shape or the like because Ge is a semimetal. Therefore, productivity or poor yield is a cause of cost increase.
Au-Sn合金即使非為Au-Ge合金亦難以加工，加工成預成型材料等時之生產性或收率差。亦即，Au-20質量%Sn雖說為共晶點之組成，但係由金屬間化合物所構成。因此，位錯難移動，因而難以變形，較薄地壓延，或加壓沖打時，容易發生龜裂或毛邊。 The Au-Sn alloy is difficult to process even if it is not an Au-Ge alloy, and has poor productivity or yield when processed into a preformed material or the like. That is, although the Au-20% by mass Sn is a composition of a eutectic point, it is composed of an intermetallic compound. Therefore, it is difficult to move the dislocations, and thus it is difficult to deform, and when it is thinly rolled or pressed, it is likely to be cracked or burred.
當然，Au系焊料合金時，材料成本與其他焊料合金相比，錯位較高。Au-Sn合金活用其熔點或加工性，大多使用作為尤其要求高信賴性之石英裝置密封用。而且，為使該Au-Sn合金便宜而更易於使用，而開發如下之Au系焊料合金。 Of course, when the Au-based solder alloy is used, the material cost is higher than that of other solder alloys. Au-Sn alloys are used in their melting point or processability, and are often used as a sealing device for quartz devices which require high reliability. Further, in order to make the Au-Sn alloy cheaper and easier to use, the following Au-based solder alloy was developed.
專利文獻5中，揭示焊材，其特徵為組成比(Au(wt%),Ag(wt%),Sn(wt%))於Au、Ag、Sn之三元組成圖中，位於下列各點所包圍之區域內： Patent Document 5 discloses a welding consumable characterized by a composition ratio (Au (wt%), Ag (wt%), Sn (wt%)) in a ternary composition diagram of Au, Ag, and Sn, which is located at the following points Within the enclosed area:
點A1(41.8,7.6,50.5) Point A1 (41.8, 7.6, 50.5)
點A2(62.6,3.4,34.0) Point A2 (62.6, 3.4, 34.0)
點A3(75.7,3.2,21.1) Point A3 (75.7, 3.2, 21.1)
點A4(53.6,22.1,24.3) Point A4 (53.6, 22.1, 24.3)
點A5(30.3,33.2,36.6)。 Point A5 (30.3, 33.2, 36.6).
該文獻之發明之目的係提供較低熔點、處理容易、強 度、接著性優異且便宜之焊材及壓電裝置。 The object of the invention is to provide a lower melting point, easy to handle, and strong Welding consumables and piezoelectric devices that are excellent in degree and adhesion and are inexpensive.
專利文獻6中揭示熔融密封用高溫無Pb焊料合金，其特徵係由Ag 2~12質量%、Au 40~55質量%，其餘部分Sn所成。 Patent Document 6 discloses a high-temperature Pb-free solder alloy for melt sealing, which is characterized in that Ag is 2 to 12% by mass, Au is 40 to 55% by mass, and the remaining portion is Sn.
該文獻之發明之目的在於提供不僅Au添加量少於以往之Au-Sn共晶合金，且固相線溫度亦為270℃以上之無Pb之高溫焊料。且，目的在於提供容器本體與蓋構件間之接合部之耐熱循環或機械強度優異之封裝。 The object of the invention is to provide a Pb-free high-temperature solder which is not only added in an amount less than the conventional Au-Sn eutectic alloy, but also has a solidus temperature of 270 ° C or higher. Further, it is an object of the invention to provide a package excellent in heat resistance cycle or mechanical strength of a joint portion between a container body and a lid member.
又，專利文獻7中，揭示Au-Sn合金焊膏，其特徵為含有(A)相對於Au與Sn之合計100質量份，Sn含55~70質量份之Au-Sn混合粉末，與(B)助焊劑， Further, Patent Document 7 discloses an Au-Sn alloy solder paste comprising (A) a total of 100 parts by mass of Au and Sn, and 55 to 70 parts by mass of Sn of Au-Sn mixed powder, and (B). ) flux,
成分(A)包含(A1)相對於Au與Sn之合計100質量份，Sn含18~23.5質量份之Au-Sn合金焊料粉末，及(A2)相對於Au與Sn之合計100質量份，Sn含88~92質量份之Au-Sn合金焊料粉末。 The component (A) contains (A1) in an amount of 100 parts by mass in total of Au and Sn, Sn in an amount of 18 to 23.5 parts by mass of Au-Sn alloy solder powder, and (A2) in 100 parts by mass in total of Au and Sn, Sn. It contains 88 to 92 parts by mass of Au-Sn alloy solder powder.
該文獻之發明係可在280℃以下之低溫接合之Au-Sn合金焊膏，且藉由該焊膏形成之Au-Sn合金焊料於Sn-Ag系無Pb焊料之二次回焊時亦不熔融。目的在於提供對於LED元件可優異接合且二次回焊時亦不熔融，因低Au化而可減低材料成本之Au-Sn合金焊膏。 The invention of this document is an Au-Sn alloy solder paste which can be bonded at a low temperature of 280 ° C or lower, and the Au-Sn alloy solder formed by the solder paste is not melted in the secondary reflow of the Sn-Ag-based Pb-free solder. . The object of the present invention is to provide an Au-Sn alloy solder paste which can be excellently bonded to an LED element and which is not melted at the time of secondary reflow, and which can reduce material cost due to low Au.
[專利文獻1]日本特開平11-77366號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-77366
[專利文獻2]日本特開平8-215880號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 8-215880
[專利文獻3]日本特開2002-160089號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-160089
[專利文獻4]日本特開2006-167790號公報 [Patent Document 4] Japanese Laid-Open Patent Publication No. 2006-167790
[專利文獻5]日本特開2008-155221號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-155221
[專利文獻6]日本專利第4305511號公報 [Patent Document 6] Japanese Patent No. 4305511
[專利文獻7]日本特開2011-167761號公報 [Patent Document 7] Japanese Laid-Open Patent Publication No. 2011-167761
關於高溫用之無Pb焊料合金除上述專利文獻以外，雖已由各種機構開發，但尚未見到低成本且廣泛使用性之焊料合金。亦即，於一般之電子零件或基板大多使用熱塑性樹脂或熱硬化性樹脂等之耐熱溫度較低之材料。因此，作業溫度必須未達400℃，期望為370℃以下。然而，使用例如專利文獻3中揭示之Bi/Ag合金作為焊材時，液相線溫度高如400~700℃。因此，接合時之作業溫度亦為400~700℃以上，會超過欲接合之電子零件或基板之耐熱溫度。 The Pb-free solder alloy for high temperature has been developed by various mechanisms in addition to the above-mentioned patent documents, but a solder alloy which is low in cost and widely used has not been seen. In other words, a material having a low heat resistance temperature such as a thermoplastic resin or a thermosetting resin is often used for a general electronic component or a substrate. Therefore, the operating temperature must be less than 400 ° C, and it is expected to be 370 ° C or less. However, when a Bi/Ag alloy disclosed in, for example, Patent Document 3 is used as the welding material, the liquidus temperature is as high as 400 to 700 °C. Therefore, the operating temperature at the time of bonding is also 400 to 700 ° C or more, which exceeds the heat resistant temperature of the electronic component or substrate to be joined.
實用化之Au-Sn系焊料合金或Au-Ge焊料合金已使用於石英裝置、SAW過濾器及MEMS等之尤其需要高信賴性之部位之焊接。然而，Au系焊料合金由於大量使用非常昂貴之Au，故與廣泛使用之Pb系焊料合金或Sn系焊料合金等比較為非常昂貴，難以說可廣泛一般使用。此外，Au系焊料合金非常硬，難以加工。因此，例 如壓延加工成薄片形狀時耗費時間，於輥必須使用難以有傷痕之特殊材質者，而增加成本。且，加壓成形時亦由於Au系焊料合金硬且脆之性質，而容易發生龜裂或毛邊。因此，與其他焊料合金相比收率顯著較低。加工成線形狀時亦有類似嚴重問題，即使使用非常高壓力之擠出機亦由於硬而使擠出速度慢，生產性僅為Pb系焊料合金之數百分之一左右。 The practical Au-Sn-based solder alloy or Au-Ge solder alloy has been used for welding of parts such as quartz devices, SAW filters, and MEMS which require high reliability. However, since the Au-based solder alloy uses a very expensive amount of Au, it is very expensive compared with a widely used Pb-based solder alloy or a Sn-based solder alloy, and it is difficult to say that it can be widely used. In addition, the Au-based solder alloy is very hard and difficult to process. Therefore, for example It takes time to calender into a sheet shape, and it is necessary to use a special material which is difficult to be scratched on the roll, and the cost is increased. Further, in the case of press molding, the Au-based solder alloy is hard and brittle, and cracks or burrs are likely to occur. Therefore, the yield is significantly lower compared to other solder alloys. There are similar serious problems when processed into a line shape. Even if a very high pressure extruder is used, the extrusion speed is slow due to hardness, and the productivity is only about one percent of the Pb-based solder alloy.
包含如上述問題在內，Au系焊料合金根據用途或使用時形狀等亦有多種問題。為了解決此等問題，已揭示例如專利文獻5所示之技術。亦即，專利文獻5中述及提供熔點較低而易於處理、強度及接著性優異且便宜之焊材以及壓電裝置。進而亦述及藉由限定Au、Sn、Ag個別之組成範圍，而比以往更減少Au含量，且可獲得作為密封材同等特性。 In addition to the above problems, the Au-based solder alloy has various problems depending on the use or the shape at the time of use. In order to solve such problems, for example, the technique shown in Patent Document 5 has been disclosed. In other words, Patent Document 5 describes a welding material and a piezoelectric device which are low in melting point and easy to handle, excellent in strength and adhesion, and inexpensive. Further, by limiting the composition range of each of Au, Sn, and Ag, the Au content is reduced more than ever, and the same characteristics as the sealing material can be obtained.
然而，並未記載藉由添加Ag而提高Au-Sn合金之強度或接著性之理由。且，亦未記載獲得作為密封材同等特性(可解釋為與Au-Ge合金同等特性)之理由。亦即，關於獲得Au-Ge共晶合金或Au-Sn共晶合晶同等特性例如獲得同等信賴性之理由則全然未記載，發明技術之根據不明確。而且基於以下所述理由不用說包含信賴性等比Au-Ge共晶合金或Au-Sn共晶合金更優異，認為於專利文獻5所示之廣泛組成範圍之全部區域中亦無法獲得與Au-Ge共晶合金或Au-Sn共晶合金同等之相同特性。 However, the reason for improving the strength or adhesion of the Au-Sn alloy by adding Ag is not described. Further, the reason why the same characteristics as the sealing material (which can be interpreted as having the same characteristics as those of the Au-Ge alloy) is not described. That is, the reason why the equivalent property of the Au-Ge eutectic alloy or the Au-Sn eutectic crystal is obtained, for example, the equivalent reliability is not described at all, and the basis of the invention is not clear. Further, for the reason described below, it is needless to say that the reliability is equal to that of the Au-Ge eutectic alloy or the Au-Sn eutectic alloy, and it is considered that the Au-Sn eutectic alloy is not available in all regions of the wide range of composition shown in Patent Document 5. The Ge eutectic alloy or the Au-Sn eutectic alloy has the same characteristics.
以下，針對認為專利文獻5之技術無法獲得 相同特性之理由加以說明。專利文獻5中，組成比(Au(wt%),Ag(wt%),Sn(wt%))於Au、Ag、Sn之三元組成圖中，位於下列各點所包圍之區域內： Hereinafter, it is considered that the technique of Patent Document 5 cannot be obtained. The reason for the same characteristics will be explained. In Patent Document 5, the composition ratio (Au (wt%), Ag (wt%), and Sn (wt%)) in the ternary composition diagram of Au, Ag, and Sn is located in the area surrounded by the following points:
點A1(41.8,7.6,50.5) Point A1 (41.8, 7.6, 50.5)
點A2(62.6,3.4,34.0) Point A2 (62.6, 3.4, 34.0)
點A3(75.7,3.2,21.1) Point A3 (75.7, 3.2, 21.1)
點A4(53.6,22.1,24.3) Point A4 (53.6, 22.1, 24.3)
點A5(30.3,33.2,36.6)。 Point A5 (30.3, 33.2, 36.6).
然而，該區域範圍過大，理論上不可能在如此廣之組成範圍所有區域均可獲得目的之相同特性。例如點A3與點A5之Au含量差45.4質量%。Au含量有如此大差異時，終究無法認為在點A3與點A5可獲得類似特性。Au、Sn、Ag之組成比若不同則產生之金屬間化合物不同，液相線溫度或固相線溫度亦大為不同。最難氧化之Au含量亦有45.4質量%不同當然潤濕性亦會大幅改變。接合時生成之金屬間化合物種類或其量亦大為不同，於如專利文獻5所示之廣範圍內並非可實現加工性及應力緩和性同樣之優異特性者。 However, the extent of the area is too large and it is theoretically impossible to obtain the same characteristics of interest in all areas of such a wide range of composition. For example, the Au content of the point A3 and the point A5 is 45.4% by mass. When there is such a large difference in the Au content, it is impossible to conclude that similar characteristics can be obtained at the point A3 and the point A5. When the composition ratios of Au, Sn, and Ag are different, the intermetallic compounds are different, and the liquidus temperature or the solidus temperature is also greatly different. The most difficult to oxidize Au content is also 45.4% by mass. Of course, the wettability will also change significantly. The type of the intermetallic compound which is formed at the time of the bonding or the amount thereof is also greatly different, and the same excellent properties as the workability and the stress relaxation property are not achieved in a wide range as shown in Patent Document 5.
專利文獻6中記載之焊材係記載為Ag為2~12質量%，Au為40~55質量%，其餘為Sn所成之焊料合金。由該種Au-Sn-Ag所成之焊料合金時，Ag含量於2~12質量%之範圍內，無法獲得由ε相與δ相所成之較細金屬組織，會成為加工性或應力緩和性等不充分之焊料合金。再者由於液相線溫度與固相線溫度之差較大，故產生 接合時之分熔現象，而有無法獲得充分接合信賴性之情況。 The welding material described in Patent Document 6 describes that the Ag is 2 to 12% by mass, the Au is 40 to 55% by mass, and the rest is a solder alloy formed of Sn. In the case of the solder alloy formed of the Au-Sn-Ag, the Ag content is in the range of 2 to 12% by mass, and a fine metal structure composed of the ε phase and the δ phase cannot be obtained, which may become workability or stress relaxation. Insufficient solder alloys. Furthermore, since the difference between the liquidus temperature and the solidus temperature is large, it is generated. There is a phenomenon of partial melting at the time of joining, and there is a case where sufficient joint reliability cannot be obtained.
專利文獻7中記載低Au且低成本之Au-Sn焊膏。關於如此之Au系焊料合金，低成本化為重要課題，根據市場要求以使技術進步時為非常重要。然而，關於專利文獻7中記載之技術，可謂存在非常大的問題。 Patent Document 7 describes a low Au and low cost Au-Sn solder paste. Regarding such an Au-based solder alloy, cost reduction is an important issue, and it is very important to advance the technology according to market requirements. However, the technique described in Patent Document 7 has a very large problem.
亦即，焊料合金粉末使用由2種組成所成之Au-Sn合金時，無法僅使該等焊料合金粉末混合即可改變各個組成之合金粉末熔點。因此，2種合金組成熔融時若無法充分混合，則硬化後亦有存在(A2)(Sn=約90%)之低熔點相之情況，作為高溫用焊膏使用時有發生問題之情況。 In other words, when the Au-Sn alloy composed of two kinds of compositions is used as the solder alloy powder, the melting point of the alloy powder of each composition can be changed by merely mixing the solder alloy powders. Therefore, if the two alloy compositions are not sufficiently mixed when melted, there is a case where a low melting point phase of (A2) (Sn = about 90%) is present after curing, and there is a problem in use as a solder paste for high temperature.
專利文獻7中記載「本發明之包含成分(A1)與成分(A2)之Au-Sn合金焊膏可使LED等半導體元件與基板接合之機制並不明確，但認為係藉由於260~280℃加熱，首先成分(A2)熔融，潤濕LED等之半導體元件、基板等被黏著物，隨後，藉由熔融之成分(A2)與成分(A1)之間之擴散，使成分(A2)與成分(A1)混合而形成Au-Sn合金焊料。藉由該機制，可實現可使LED元件易於藉由在280℃以下之加熱而接合，且可形成接合後之固相線溫度為250℃以上之Au-Sn合金焊料之Au-Sn合金焊膏」。 Patent Document 7 describes that the mechanism of joining the semiconductor element such as an LED to a substrate by the Au-Sn alloy solder paste containing the component (A1) and the component (A2) of the present invention is not clear, but it is considered to be due to 260 to 280 ° C. Heating, first, the component (A2) is melted, and the adherend such as a semiconductor element or a substrate such as an LED is wetted, and then the component (A2) and the component are diffused by the diffusion between the molten component (A2) and the component (A1). (A1) mixing to form an Au-Sn alloy solder. By this mechanism, it is possible to easily bond the LED element by heating at 280 ° C or lower, and the solidus temperature after bonding can be 250 ° C or higher. Au-Sn alloy solder paste for Au-Sn alloy.
然而，假定富含Sn之(A2)成分熔解，與接近Au-Sn共晶點之成分(A1)擴散接合時，接合部之Au-Sn合金會大幅偏離共晶點之組成。若如此，則組織不為層狀組織，而成為以非常硬且脆之相構成組織之大部分，而無應力緩和 特性等，認為接合信賴性亦非常低。因此，以降低Au含量而降低焊膏之成本之觀點雖為非常優異，但基於上述理由並非實用技術。 However, assuming that the Sn-rich (A2) component is melted and diffusely bonded to the component (A1) close to the Au-Sn eutectic point, the Au-Sn alloy at the joint greatly deviates from the composition of the eutectic point. If so, the tissue is not layered, but becomes the majority of the tissue in a very hard and brittle phase without stress relief. Characteristics, etc., and the joint reliability is considered to be very low. Therefore, although the viewpoint of reducing the Au content and reducing the cost of the solder paste is very excellent, it is not a practical technique based on the above reasons.
Au系焊料合金包含焊膏而改如上述有應進行各種改善之課題。本發明係鑑於上述課題而完成者，目的在於提供於石英裝置、SAW過濾器或MEMS等要求非常高信賴性之接合或密封中亦可充分使用之各種特性優異之高溫用Au-Sn-Ag系焊膏，由其提供低成本且具有良好潤濕性且應力緩和性、接合信賴性等優異之無Pb之焊膏。 The Au-based solder alloy contains a solder paste and is subject to various improvements as described above. The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an Au-Sn-Ag system for high-temperature use which is excellent in various characteristics such as a quartz device, a SAW filter, or a MEMS which are required to be highly reliable in bonding or sealing. The solder paste is provided with a Pb-free solder paste which is excellent in low cost and has good wettability, stress relaxation property, bonding reliability, and the like.
為達成上述目的，本發明之不含Pb之Au-Sn-Ag系焊膏，係使焊料合金粉末與助焊劑混合而成之焊膏，其特徵為該焊料合金粉末以其合計設為100質量%時，含有超過38.0質量%且43.0質量%以下之Sn，含有超過12.0質量%且15.0質量%以下之Ag，其餘部分除製造上不可避免所含之元素以外，係由Au所成。 In order to achieve the above object, the Pb-free Au-Sn-Ag solder paste of the present invention is a solder paste obtained by mixing a solder alloy powder and a flux, and is characterized in that the solder alloy powder is set to 100 mass in total. In the case of %, more than 38.0% by mass and 43.0% by mass or less of Sn is contained, and more than 12.0% by mass and 15.0% by mass or less of Ag is contained, and the remainder is formed of Au in addition to the elements which are inevitably contained in the production.
又，本發明之不含Pb之Au-Sn-Ag系焊膏係前述助焊劑含有松脂。 Further, the Pb-free Au-Sn-Ag-based solder paste of the present invention contains the rosin as the flux.
又，本發明之不含Pb之Au-Sn-Ag系焊膏係前述焊料合金粉末含有超過38.0質量%且41.0質量%以下之Sn，含有12.5質量%以上且14.5質量%以下之Ag，其餘部分除製造上不可避免所含之元素以外，係由Au所成。 In addition, the Pb-free Au-Sn-Ag-based solder paste of the present invention contains more than 38.0% by mass and 41.0% by mass or less of Sn, and contains 12.5% by mass or more and 14.5% by mass or less of Ag, and the rest. In addition to the elements that are inevitably contained in the manufacture, it is made of Au.
又，本發明提供Si半導體元件接合體，其特徵係使用上述之不含Pb之Au-Sn-Ag系焊膏接合而成。 Moreover, the present invention provides a Si semiconductor element bonded body characterized in that the above-described Au-Sn-Ag-based solder paste containing no Pb is bonded.
又，本發明提供石英振盪器密封元件，其特徵係使用上述之不含Pb之Au-Sn-Ag系焊膏密封而成。 Further, the present invention provides a quartz oscillator sealing member characterized by being sealed with the above-mentioned Pb-free Au-Sn-Ag-based solder paste.
依據本發明，可比以往之Au係焊膏格外便宜地提供使用於石英裝置、SAW過濾器以及MEMS等之要求非常高信賴性之部位之焊膏。再者，本發明之焊膏中使用之焊料合金係以柔軟性較高之ε相與δ相為基本，應力緩和性、接合信賴性優異且具有於Au-12.5質量%Ge焊料合金之熔點與Au-20質量%Sn焊料合金之熔點之間之較佳熔點。且，因成為與助焊劑混合之焊膏之形態，而可提供具有更優異潤濕性之Au系焊膏。因此，工業貢獻度極高。 According to the present invention, it is possible to provide a solder paste which is used in a site requiring a very high reliability such as a quartz device, a SAW filter, and a MEMS, which is particularly inexpensive, compared with the conventional Au-based solder paste. Further, the solder alloy used in the solder paste of the present invention is based on the ε phase and the δ phase having high flexibility, and is excellent in stress relaxation property and bonding reliability, and has a melting point of Au-12.5 mass% Ge solder alloy. A preferred melting point between the melting points of the Au-20% by mass solder alloy. Further, since it is in the form of a solder paste mixed with a flux, an Au-based solder paste having more excellent wettability can be provided. Therefore, the industrial contribution is extremely high.
1‧‧‧Cu基板 1‧‧‧Cu substrate
2‧‧‧Ni層 2‧‧‧Ni layer
3‧‧‧焊料合金 3‧‧‧ solder alloy
4‧‧‧Si晶片 4‧‧‧Si chip
5‧‧‧石英振盪器 5‧‧‧Crystal Oscillator
6‧‧‧導電性接著劑 6‧‧‧ Conductive adhesive
7‧‧‧端子 7‧‧‧ Terminal
8‧‧‧密封用蓋 8‧‧‧ Sealing cover
9‧‧‧密封用容器 9‧‧‧Seal container
圖1係Au-Sn-Ag三元系狀態圖。 Figure 1 is a state diagram of the Au-Sn-Ag ternary system.
圖2係示意性顯示於具有Ni層之Cu基板上焊接焊料合金之潤濕性試驗之實施形態之剖面圖。 Fig. 2 is a cross-sectional view showing an embodiment of a wettability test for soldering a solder alloy on a Cu substrate having a Ni layer.
圖3係示意性顯示圖2之潤濕性試驗之縱橫比測定狀態之側視圖。 Fig. 3 is a side view schematically showing the aspect ratio measurement state of the wettability test of Fig. 2.
圖4係示意性顯示於具有Ni層之Cu基板上使用焊料 合金接合Si晶片之接合體之剖面圖。 Figure 4 is a schematic view showing the use of solder on a Cu substrate having a Ni layer A cross-sectional view of a bonded body of an alloy bonded Si wafer.
圖5係示意性顯示石英振盪器封裝之剖面圖。 Figure 5 is a cross-sectional view schematically showing a quartz oscillator package.
本發明重複積極研究之結果，發現藉由使ε相(以at%計Au：Sn：Ag=16.1：21.5：62.4)與δ相(Au1Sn1金屬間化合物)為基本之Au-Sn-Ag系焊料合金粉末，具體為含有超過38.0質量%且43.0質量%以下之Sn，含有超過12.0質量%且15.0質量%以下之Ag，其餘部分除製造上不可避免所含之元素以外，係由Au構成之焊料合金粉末與助焊劑混合之焊膏形態，該焊膏具有如下之特性或效果，因而完成本發明。 The present invention repeats the results of active research and finds that Au-Sn- is based on the ε phase (Au:Sn:Ag=16.1:21.5:62.4 in at%) and the δ phase (Au 1 Sn 1 intermetallic compound). Specifically, the Ag-based solder alloy powder contains more than 38.0% by mass and 43.0% by mass or less of Sn, and contains more than 12.0% by mass and 15.0% by mass or less of Ag, and the rest is made of Au in addition to elements which are inevitably contained in the production. The solder paste composition of the solder alloy powder and the flux is mixed, and the solder paste has the following characteristics or effects, and thus the present invention has been completed.
亦即，滿足本發明之組成範圍之焊料合金，與Au-20質量%Sn合金相比更柔軟，因此應力緩和性、接合信賴性優異且昂貴之Au之一部分由Sn與Ag代替而將Au含量大幅降低至50質量%以下而可降低合金成本。再者，可為具有於Au-12.5質量%Ge焊料合金之熔點與Au-20質量%Sn焊料合金之熔點之間之較佳熔點者。藉由成為使該焊料合金粉末與助焊劑混合之焊膏形態，可成為潤濕性、接合性更優異之接合材。 That is, the solder alloy satisfying the composition range of the present invention is softer than the Au-20% by mass Sn alloy, and therefore the stress relaxation property and the joint reliability are excellent, and one part of the expensive Au is replaced by Sn and Ag to form the Au content. The alloy cost can be reduced by drastically reducing it to 50% by mass or less. Further, it may be a preferred melting point between the melting point of the Au-12.5 mass% Ge solder alloy and the melting point of the Au-20 mass% Sn solder alloy. By forming the solder paste in which the solder alloy powder and the flux are mixed, it is possible to obtain a bonding material which is more excellent in wettability and bonding property.
以下，針對本發明之Au-Sn-Ag系焊膏詳細說明。本發明之Au-Sn-Ag系焊料合金之組成之特徵係含有超過38.0質量%且43.0質量%以下之Sn，含有超過12.0質量%且15.0質量%以下之Ag，其餘部分除製造上不可 避免所含之元素以外，係由Au構成。 Hereinafter, the Au-Sn-Ag-based solder paste of the present invention will be described in detail. The composition of the Au-Sn-Ag-based solder alloy of the present invention is characterized in that it contains more than 38.0% by mass and 43.0% by mass or less of Sn, and contains more than 12.0% by mass and 15.0% by mass or less of Ag, and the remainder is not manufactured. In addition to the elements contained, it is composed of Au.
本發明之焊膏中使用之焊料合金為了大幅降低非常高成本的Au系焊料合金之成本同時具有優異之柔軟性與應力緩和性，而含有伸長率比Au等更高之金屬的Ag且以具有比較柔軟性之ε相作為構成要素之一。亦即本發明之Au-Sn-Ag系合金於自液體狀態冷卻為固體時，首先自液相析出ζ相(以at%計Au：Sn：Ag=30.1：16.1：53.8)，隨後，進行冷卻時，自液相+ζ相析出ε相與δ相之2相。而且，由於液相線溫度與固相線溫度比較接近，故該ε相與δ相之金屬組織比較細。而且加上ε相具有較柔軟性，而成為作為焊料合金之加工性或應力緩和性等優異之材料。而且，由於含有反應性高之Ag等而可成為潤濕性或接合性亦優異之焊料合金。而且，具有於Au-Ge焊料合金之熔點與Au-Sn焊料合金之熔點之間之較佳熔點。再者，因與助焊劑混合成為焊膏，故形狀自由度變大，成為潤濕擴展性、接合信賴性等優異之接合材。以下，針對本發明之焊料合金中之必須元素以及助焊劑進一步詳細說明。 The solder alloy used in the solder paste of the present invention has a high flexibility and stress relaxation property in order to greatly reduce the cost of a very high cost Au-based solder alloy, and contains Ag of a metal having a higher elongation than Au and the like. The ε phase of comparative softness is one of the constituent elements. In other words, when the Au-Sn-Ag alloy of the present invention is cooled from a liquid state to a solid, the ruthenium phase (A:Sn:Ag=30.1:16.1:53.8 in at%) is first precipitated from the liquid phase, followed by cooling. At the same time, two phases of the ε phase and the δ phase are precipitated from the liquid phase + ζ phase. Moreover, since the liquidus temperature is close to the solidus temperature, the metal structure of the ε phase and the δ phase is relatively fine. Further, the ε phase has flexibility, and is excellent as a workability or stress relaxation property of the solder alloy. In addition, it is a solder alloy which is excellent in wettability and bonding property because it contains Ag or the like having high reactivity. Moreover, it has a preferred melting point between the melting point of the Au-Ge solder alloy and the melting point of the Au-Sn solder alloy. In addition, since it is mixed with a flux to form a solder paste, the degree of freedom in shape is increased, and it is excellent in wettability, bonding reliability, and the like. Hereinafter, the essential elements and the flux in the solder alloy of the present invention will be described in further detail.
Au係本發明中使用之焊料合金之主成分，且當然為必須成分。Au由於非常不易氧化，故作為要求高信賴性之電子零件類之接合或密封用之焊料合金成分，就特性面而言最適合。因此，作為石英裝置或SAW過濾器之密封 用大多使用Au系焊料合金。本發明中使用之焊料合金亦以Au為基本，而提供屬於要求如此高信賴性之技術領域之焊料合金。惟，由於Au為非常昂貴之金屬，故就成本方面較好儘可能不用。因此，於要求一般等級之信賴性之電子零件中不使用焊料。本發明中使用之焊料合金之潤濕性或接合性之特性為與Au-20質量%Sn焊料合金或Au-12.5質量%Ge焊料合金為同等以上。且，為了提高柔軟性、加工性，此外減低Au含量並降低成本，而設為主要由ε相與δ相構成之Au-Sn-Ag系合金。 Au is a main component of the solder alloy used in the present invention, and is of course an essential component. Since Au is very resistant to oxidation, it is most suitable for the characteristic surface as a solder alloy component for bonding or sealing of electronic parts requiring high reliability. Therefore, as a seal for quartz or SAW filters Most of the use is an Au-based solder alloy. The solder alloy used in the present invention is also based on Au, and provides a solder alloy belonging to the technical field requiring such high reliability. However, since Au is a very expensive metal, it is better to use it as much as possible. Therefore, solder is not used in electronic parts that require a general level of reliability. The solder alloy used in the present invention has properties of wettability or bondability equal to or higher than that of the Au-20% by mass solder alloy or the Au-12.5 mass% Ge solder alloy. In addition, in order to improve the flexibility and workability, and to reduce the Au content and reduce the cost, an Au-Sn-Ag alloy mainly composed of an ε phase and a δ phase is used.
Sn係本發明中使用之焊料合金中之必須元素，係成為基本之元素。Au-Sn焊料合金通常以共晶點附近之組成，亦即Au-20質量%Sn附近之組成使用。藉此，固相線溫度為280℃且結晶微細化，獲得較柔軟性。然而，亦稱為共晶合金之Au-20質量%Sn合金由於由Au1Sn1金屬間化合物與Au5Sn1金屬間化合物所構成，故硬且脆。因此，難以加工，例如藉由壓延加工成薄片狀時，只能一點一點慢慢變薄。因此，生產性差，壓延時產生多數龜裂而使收率惡化，金屬間化合物之硬且脆之性質通常無法改變。雖為如此硬且脆之材料，但由於不易氧化且潤濕性、信賴性優異，故使用於要求高信賴性之用途。 Sn is an essential element in the solder alloy used in the present invention and is a basic element. The Au-Sn solder alloy is usually used in a composition in the vicinity of the eutectic point, that is, in the vicinity of Au-20% by mass Sn. Thereby, the solidus temperature was 280 ° C and the crystals were refined to obtain softness. However, the Au-20% by mass Sn alloy, which is also called a eutectic alloy, is hard and brittle because it is composed of an Au 1 Sn 1 intermetallic compound and an Au 5 Sn 1 intermetallic compound. Therefore, it is difficult to process, for example, when it is processed into a sheet by calendering, it can be gradually thinned little by little. Therefore, the productivity is poor, the cracking causes most cracks to deteriorate the yield, and the hard and brittle nature of the intermetallic compound cannot usually be changed. Although it is such a hard and brittle material, it is difficult to oxidize and has excellent wettability and reliability, so it is used in applications requiring high reliability.
本發明中使用之焊料合金係由ε相(ε相係Au-Sn-Ag金屬間化合物，其組成比例以at%計Au：Sn：Ag=16.1： 21.5：62.4。參考文獻：Ternary Alloys,A Comprehensive Compendium of Evaluated Constitutional Data and Phase Diagrams，由G.Petzow及Effenberg編輯，VCH)與δ相(Au1Sn1金屬間化合物)構成。該ε相具有比較柔軟性，而且液相線溫度與固相線溫度比較接近，故本發明中使用之焊料合金成為加工性、應力緩和性等優異。本發明中使用之焊料合金具有比Au-12.5質量%Ge合金之共晶溫度356度低，且比Au-20質量%Sn合金之共晶溫度280℃高的351℃之固相線溫度。具有於該Au-12.5質量%Ge合金之共晶溫度與Au-20質量%Sn合金之共晶溫度之間之熔點具有非常重要之意義。亦即，根據用途，對於具有於Au-12.5質量%Ge焊料合金與Au-20質量%焊料合金之間之熔點的焊料合金有需求，但可與此對應之焊料合金過去僅有Pb系焊料合金，並不存在顧慮到環境面之焊料合金。具備具有作為此種高溫用焊料合金之優異特徵之熔點為本發明中使用之焊料合金之較大優點之一。進而，由於熔點低於Au-12.5質量%Ge合金之共晶溫度356℃，故可於比Au-12.5質量%Ge合金更低溫製造，就成本面或安全面亦有優勢。 The solder alloy used in the present invention is composed of an ε phase (ε phase system Au-Sn-Ag intermetallic compound, the composition ratio of which is in atom% Au:Sn:Ag=16.1: 21.5:62.4. Reference: Ternary Alloys, A Comprehensive Compendium of Evaluated Constitutional Data and Phase Diagrams, edited by G. Petzow and Effenberg, VCH) and δ phase (Au 1 Sn 1 intermetallic compound). Since the ε phase has relatively high flexibility and the liquidus temperature is close to the solidus temperature, the solder alloy used in the present invention is excellent in workability, stress relaxation, and the like. The solder alloy used in the present invention has a solidus temperature lower than the eutectic temperature of Au-12.5 mass% Ge alloy by 356 degrees and 351 °C higher than the eutectic temperature of 280 °C of the Au-20 mass% Sn alloy. It is very important to have a melting point between the eutectic temperature of the Au-12.5 mass% Ge alloy and the eutectic temperature of the Au-20 mass% Sn alloy. That is, depending on the use, there is a demand for a solder alloy having a melting point between Au-12.5 mass% Ge solder alloy and Au-20 mass% solder alloy, but the solder alloy corresponding thereto has only Pb solder alloy in the past. There is no solder alloy that is concerned about the environment. It is one of the great advantages of having a melting point which is an excellent characteristic of such a high-temperature solder alloy as the solder alloy used in the present invention. Further, since the melting point is lower than the eutectic temperature of 356 ° C of the Au-12.5 mass% Ge alloy, it can be produced at a lower temperature than the Au-12.5 mass% Ge alloy, and it is also advantageous in terms of the cost surface or the safety surface.
Sn含量超過38.0質量%且43.0質量%以下。若為38.0質量%以下，則結晶粒變大，無法充分發揮柔軟性、加工性提高等之效果。此外，液相線溫度與固相線溫度之差過大而產生分熔現象等。進而由於Au含量亦容易變多亦限定了成本削減效果。另一方面，Sn含量超過43.0質 量%時，過於偏離ε相與δ相之混合組成而使結晶粒粗大化，產生液相線溫度與固相線溫度之差增大之問題。此外，由於Sn含量變過多，故氧化之可能性提高，而失去Au系焊料合金之特徵的良好潤濕性，因此有難以獲得高的接合信賴性之情況。 The Sn content is more than 38.0% by mass and 43.0% by mass or less. When it is 38.0% by mass or less, the crystal grains become large, and effects such as improvement in flexibility and workability cannot be sufficiently exhibited. Further, the difference between the liquidus temperature and the solidus temperature is too large to cause a melting phenomenon or the like. Further, since the Au content is also likely to increase, the cost reduction effect is also limited. On the other hand, the Sn content exceeds 43.0 When the amount is %, the mixture of the ε phase and the δ phase is excessively deviated to coarsen the crystal grains, and the difference between the liquidus temperature and the solidus temperature is increased. Further, since the Sn content is excessively increased, the possibility of oxidation is increased, and the good wettability characteristic of the Au-based solder alloy is lost, so that it is difficult to obtain high joint reliability.
Sn含量若為超過38.0質量%且41.0質量%以下，則更進一步成為ε相與δ相充分混合之組成，使結晶粒更微細化且使液相線溫度與固相線溫度之差減小故不易產生分熔現象而較佳。 When the Sn content is more than 38.0% by mass and 41.0% by mass or less, the composition in which the ε phase and the δ phase are sufficiently mixed is further formed, and the crystal grains are made finer and the difference between the liquidus temperature and the solidus temperature is decreased. It is preferable that the melting phenomenon is not easily generated.
Ag係本發明中使用之焊料合金中之必須元素，係具有將熔點調整為適度溫度，確保潤濕性，有助於減低成本等之重要效果的元素。藉由成為本發明之Au-Sn-Ag系合金之組成範圍，可獲得適於最初之優異柔軟性或加工性、應力緩和性之熔點等，且可大幅減低Au含量，可實現更大之成本削減。如所述Ag亦有提高潤濕性之效果。亦即Ag與基板等之最上面所使用之Cu、Ni等之反應性良好，可提高潤濕性。當然，不用說與半導體元件之接合面良好使用之Ag或Au等之金屬化層之反應性優異。 Ag is an essential element in the solder alloy used in the present invention, and has an important effect of adjusting the melting point to an appropriate temperature, ensuring wettability, and contributing to cost reduction. By setting the composition range of the Au-Sn-Ag-based alloy of the present invention, it is possible to obtain a melting point suitable for the first excellent softness, workability, stress relaxation property, etc., and to greatly reduce the Au content, thereby achieving a larger cost. reduce. As described above, Ag also has an effect of improving wettability. That is, Ag has good reactivity with Cu, Ni, or the like used for the uppermost layer of the substrate, and the like, and the wettability can be improved. Needless to say, it is needless to say that the metallization layer such as Ag or Au which is used well in the joint surface of the semiconductor element is excellent in reactivity.
具有此種優異效果之Ag含量超過12.0質量%且15.0質量%以下。為12.0質量%以下時，過於偏離形成ε相與δ相之混合相之組成，液相線溫度變得過高，結晶粒過於粗大，難以獲得良好接合。另一方面，超過15.0質量%之 情況時，液線溫度亦變高，產生分熔現象，結晶粒粗大化會成為問題。 The Ag content having such an excellent effect exceeds 12.0% by mass and 15.0% by mass or less. When it is 12.0% by mass or less, the composition of the mixed phase in which the ε phase and the δ phase are formed is excessively deviated, the liquidus temperature becomes too high, and the crystal grains are too coarse, and it is difficult to obtain good bonding. On the other hand, more than 15.0% by mass In the case of a case, the liquidus temperature also becomes high, and a melting phenomenon occurs, and coarsening of crystal grains becomes a problem.
若為12.5質量%以上且14.5質量%以下，則成為ε相與δ相充分混合之組成，可更顯現含有Ag之效果而較佳。 When it is 12.5% by mass or more and 14.5% by mass or less, the composition in which the ε phase and the δ phase are sufficiently mixed is preferable, and the effect of containing Ag is more preferable.
本發明之焊膏中使用之助熔劑種類並未特別限制，可使用例如樹脂系、無機氯化物系、有機鹵化物系等。此處，針對最一般之於助焊劑之基底材中使用松脂而於其中添加活性劑及溶劑者加以描述。 The type of the flux used in the solder paste of the present invention is not particularly limited, and for example, a resin system, an inorganic chloride system, an organic halide system or the like can be used. Here, the use of rosin in the base material most commonly used for the flux and the addition of the active agent and the solvent thereto will be described.
作為例所示之助熔劑，於將助熔劑全量設為100質量%時，基底材的松脂較好調配20~30質量%，活性劑為0.2~1質量%，溶劑為70~80質量%左右。藉此可提供具有良好潤濕性及接合性之焊膏。作為基底材之松脂亦可用例如濕樹脂松脂、橡膠松脂、妥爾油松脂等之天然未改性之松脂，亦可使用松脂酯、氫化松脂、松脂改性樹脂、聚合松脂等之改性松脂。 As a flux shown in the example, when the total amount of the flux is 100% by mass, the rosin of the base material is preferably 20 to 30% by mass, the active agent is 0.2 to 1% by mass, and the solvent is 70 to 80% by mass. . Thereby, a solder paste having good wettability and bonding property can be provided. As the rosin of the base material, natural unmodified turpentine such as wet resin rosin, rubber rosin, tall oil rosin, and the like, and modified turpentine such as rosin ester, hydrogenated rosin, rosin modified resin, and polymeric rosin may be used.
溶劑可使用丙酮、戊基苯、正戊醇、苯、四氯化碳、甲醇、乙醇、異丙醇、正丁醇、異丁醇、甲基乙基酮、甲苯、萜品油、二甲苯、環己烷、乙二醇單苯醚、乙二醇單丁醚、四氯化碳、三氯乙烷、烷二醇、伸烷二醇、丁二醇、三乙二醇、四乙二醇、十四烷等。 The solvent may be acetone, pentylbenzene, n-pentanol, benzene, carbon tetrachloride, methanol, ethanol, isopropanol, n-butanol, isobutanol, methyl ethyl ketone, toluene, terpene oil, xylene , cyclohexane, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, carbon tetrachloride, trichloroethane, alkanediol, alkylene glycol, butanediol, triethylene glycol, tetraethylene Alcohol, tetradecane, and the like.
活性劑可使用磷酸、氯化鈉、氯化銨、氯化 鋅、氯化亞錫、苯胺鹽酸鹽、聯胺鹽酸鹽、溴化乙醯基吡啶、苯基聯胺鹽酸鹽、四氯萘、甲基聯胺鹽酸鹽、甲胺鹽酸鹽、乙胺鹽酸鹽、二乙胺鹽酸鹽、丁基胺鹽酸鹽、苯甲酸、硬脂酸、乳酸、檸檬酸、草酸、琥珀酸、己二酸、癸二酸、三乙醇胺、二苯基胍、二苯基胍HBr、赤糖醇、木糖三醇、山梨醇、核糖醇等。 The active agent can be used with phosphoric acid, sodium chloride, ammonium chloride, and chlorination. Zinc, stannous chloride, aniline hydrochloride, hydrazine hydrochloride, ethidium bromide, phenyl hydrazine hydrochloride, tetrachloronaphthalene, methyl hydrazine hydrochloride, methylamine hydrochloride , ethylamine hydrochloride, diethylamine hydrochloride, butylamine hydrochloride, benzoic acid, stearic acid, lactic acid, citric acid, oxalic acid, succinic acid, adipic acid, sebacic acid, triethanolamine, two Phenylhydrazine, diphenylphosphonium HBr, erythritol, xylose, sorbitol, ribitol, and the like.
且含有搖變劑而調整搖變性時可成為更易使用之焊膏。作為搖變劑可使用例如硬脂酸醯胺、油酸醯胺、芥酸醯胺。 It also becomes a more easily used solder paste when it contains a shaker and adjusts the shake. As the rocking agent, for example, decylamine stearate, decyl oleate, guanyl erucamide can be used.
自該等溶劑及活性劑中選擇合於目的之物質，藉由適當調整該等之添加量獲得較佳之助焊劑。例如於焊料合金或基板等之接合面之氧化膜強固時，較好添加較多松脂或活性劑，以溶劑調整黏性或流動性。 A preferred flux is obtained by appropriately adjusting the amount of the solvent selected from the solvent and the active agent. For example, when the oxide film on the bonding surface of the solder alloy or the substrate is strong, it is preferred to add a large amount of rosin or an active agent to adjust the viscosity or fluidity with a solvent.
藉由使上述焊料合金與助焊劑混合而得之焊膏藉由助熔劑之作用而具備非常優異之潤濕性。此外，關於焊料合金於伴隨加工困難而無加工成薄片形狀等之必要時，可使用易於加工之粉末狀。 The solder paste obtained by mixing the above solder alloy and the flux has excellent wettability by the action of the flux. Further, when the solder alloy is not required to be processed into a sheet shape or the like due to difficulty in processing, a powder which is easy to process can be used.
而且，藉由將本發明之高溫用無Pb焊膏使用於電子零件與基板之接合，即使於反覆進行熱循環之環境等之嚴苛條件下使用時，亦可提供具有耐久性之信賴性高之電子零件用基板。因此，藉由將該電子零件用基板搭載於例如閘流電晶體或電感器等之功率半導體裝置、搭載於汽車等之各種控制裝置、太陽能電池等之在嚴苛條件下使用之裝置，可更提高該等各種裝置之信賴性。又，如此優 異之本發明焊膏非常適合作為石英振盪器之密封用，例如可使用作為如圖5所示之石英振盪器封裝之密封用。 Further, by using the high-temperature Pb-free solder paste of the present invention for bonding the electronic component and the substrate, it is possible to provide high reliability with durability even when used under severe conditions such as an environment in which thermal cycling is repeated. The substrate for electronic parts. Therefore, the electronic component substrate can be mounted on a power semiconductor device such as a thyristor or an inductor, a device mounted on various control devices such as automobiles, and a solar cell, which can be used under severe conditions. Improve the reliability of these various devices. Again, so excellent The solder paste of the present invention is very suitable as a seal for a quartz oscillator, and can be used, for example, as a seal for a quartz oscillator package as shown in FIG.
以下基於實施例更詳細說明本發明，但本發明不受該等實施例之任何限制。 The invention is illustrated in more detail below on the basis of the examples, but the invention is not limited by the examples.
首先，準備做為原料之純度分別為99.99質量%以上之Au、Sn及Ag，與比較用之Au-Ge合金用之Ge。關於較大薄片或塊狀原料，為了使熔解後之合金不會因取樣部位而組成有偏差而成為均一而進行切斷、粉碎等，切細為3mm見方以下之大小。其次，於高頻熔解爐用石墨坩堝中秤量入該等原料之特定量。 First, Au, Sn, and Ag, each having a purity of 99.99% by mass or more, and Ge for use in an Au-Ge alloy for comparison are prepared. In the case of the large-sized sheet or the bulk material, the alloy after the melting is not uniformly deformed by the sampling portion, and is cut, pulverized, etc., and is shredded to a size of 3 mm or less. Next, a specific amount of the raw materials is weighed in a graphite crucible for a high-frequency melting furnace.
將饋入原料之坩堝放入高頻熔解爐中，為了抑制氧化而對原料每1kg以0.7L/分鐘以上之流量流入氮氣。以該狀態通入熔解爐之電源，將原料加熱熔解。金屬首先熔解並以攪拌棒充分攪拌，以不引起局部組成偏差之方式均一混合。確認充分熔融後，切斷高頻電源，快速取出坩堝，將坩堝內之熱液流入焊料母合金之鑄模中。該鑄模於用以製造粉末之氣相中霧化用係使用直徑160mm之圓柱形狀者。 The crucible to which the raw material was fed was placed in a high-frequency melting furnace, and in order to suppress oxidation, nitrogen gas was introduced into the raw material at a flow rate of 0.7 L/min or more per kg. In this state, the power source of the melting furnace is passed, and the raw material is heated and melted. The metal is first melted and thoroughly stirred with a stir bar to be uniformly mixed in such a manner as not to cause local compositional deviation. After confirming that it is sufficiently melted, the high-frequency power source is cut off, the crucible is quickly taken out, and the hot liquid in the crucible is poured into the mold of the solder master alloy. The mold was used for atomization in the gas phase for producing a powder, and a cylindrical shape having a diameter of 160 mm was used.
如此，除改變原料之混合比例以外，與上述同樣，製作試料1~16之焊料母合金。針對該等試料1~16之各焊料母合金，使用ICP發光分光分析器(SHIMAZU S-8100)進行組成分析。所得分析結果示於下述表1。 Thus, the solder master alloys of the samples 1 to 16 were prepared in the same manner as above except that the mixing ratio of the raw materials was changed. For each of the solder master alloys of the samples 1 to 16, an composition analysis was performed using an ICP emission spectroscopic analyzer (SHIMAZU S-8100). The analysis results obtained are shown in Table 1 below.
焊膏用合金粉末之製造方法並未特別限定，一般為藉由霧化法製造。霧化法可於氣相中、液相中任一者中進行，只要考慮目的之焊料合金粉末之粒徑或粒度分佈等選定即可。本實施例中，藉由可製造生產性高、比較細之粉末之氣相中霧化法製作焊料合金粉末。 The method for producing the alloy powder for solder paste is not particularly limited, and is generally produced by an atomization method. The atomization method can be carried out in any one of the gas phase and the liquid phase, and may be selected in consideration of the particle size or particle size distribution of the intended solder alloy powder. In the present embodiment, the solder alloy powder is produced by a gas phase atomization method in which a highly productive and relatively fine powder can be produced.
具體而言，使用氣相中霧化裝置(日新技研股份有限 公司製)，藉由高頻熔解方式進行氣相中霧化。首先，將上述試料1~16之焊料母合金分別逐一批次進行加工。具體而言，將母合金之試料投入高頻熔解坩堝中，蓋上蓋密閉後，吹入氮氣，成為實質無氧之狀態。試料排出口或回收容器部分亦同樣吹入氮氣成為無氧狀態。 Specifically, the use of a gas phase atomization device (Nissin Technics Co., Ltd. Co., Ltd.), atomization in the gas phase by high frequency melting. First, the solder master alloys of the above samples 1 to 16 were processed one by one. Specifically, the sample of the mother alloy is placed in a high-frequency melting crucible, and the lid is sealed, and then nitrogen gas is blown to be substantially oxygen-free. The sample discharge port or the recovery container portion is also blown with nitrogen gas to be in an anaerobic state.
以該狀態切入高頻電源開關，將焊料母合金加熱至450℃以上，使以合金充分熔融之狀態以氮氣對熔融焊料母合金施加壓力，而霧化。如此製作之焊料合金粉末回收於容器中，於該容器中充分冷卻後取出至大氣中。充分冷卻後取出之理由係因為在高溫狀態下取出會起火，而使焊料合金粉末氧化使潤濕性等效果降低之故。 In this state, the high-frequency power switch is cut, and the solder master alloy is heated to 450 ° C or higher, and the molten alloy master alloy is pressurized with nitrogen gas in a state where the alloy is sufficiently melted, and atomized. The solder alloy powder thus produced is recovered in a container, sufficiently cooled in the container, and taken out to the atmosphere. The reason why it is sufficiently cooled and taken out is because the flame is removed when it is taken out at a high temperature, and the solder alloy powder is oxidized to lower the effect such as wettability.
如此製造之各粉末各以網眼20μm與50μm之篩分級，獲得直徑20~50μm之合金粉末試料。 Each of the powders thus produced was classified by a mesh of 20 μm and 50 μm, and an alloy powder sample having a diameter of 20 to 50 μm was obtained.
其次，將自焊料母合金分別製作之焊料合金粉末分別與助焊劑混合，製作焊膏。本發明中之助焊劑並未限定，但於本實施例中助焊劑係使用聚合松脂作為基底材，使用二乙胺鹽酸鹽((C2H5)2NH．HCl)作為活性劑，使用乙醇作為溶劑。各含量係將助焊劑設為100質量%，聚合松脂設為23質量%，二乙胺鹽酸鹽設為0.3質量%，其餘部分為乙醇。該助熔劑與上述焊料合金粉末係以助焊劑9.2質量%，焊料合金粉末90.8質量%之比例調和，使用小型摻合機混合作成焊膏。 Next, the solder alloy powder separately prepared from the solder master alloy is mixed with the flux to prepare a solder paste. The flux in the present invention is not limited, but in the present embodiment, the flux is polymerized rosin as a base material, and diethylamine hydrochloride ((C 2 H 5 ) 2 NH.HCl) is used as an active agent. Ethanol is used as a solvent. The content of each flux was 100% by mass, the polymerization rosin was 23% by mass, the diethylamine hydrochloride was 0.3% by mass, and the balance was ethanol. The flux and the solder alloy powder were prepared by blending a flux of 9.3% by mass and a solder alloy powder of 98.8% by mass, and mixing them by a small blender to form a solder paste.
如此，自上述表1所示之試料1~16之焊料母合金分別作成試料1~16之焊膏。而且，對於該等試料1~16之焊膏之各者進行以下所示之評價。亦即，作為潤濕性評價1係進行焊料合金粉末之未熔融確認，作為潤濕性評價2進行縱橫比之測定，作為接合性評價1進行孔隙率測定，作為接合性評價2進行剪切強度測定，作為信賴性評價進行熱循環試驗。 Thus, solder pastes of Samples 1 to 16 were prepared from the solder master alloys of Samples 1 to 16 shown in Table 1 above. Further, each of the solder pastes of the samples 1 to 16 was evaluated as described below. In the wettability evaluation 1 , the solder alloy powder was not melted, and the aspect ratio was measured as the wettability evaluation 2, and the porosity was measured as the adhesion evaluation 1 and the shear strength was measured as the adhesion evaluation 2 . The measurement was carried out as a reliability test to perform a thermal cycle test.
作為潤濕性評價1，如圖2所示般於表面具有Ni層2(層厚：約2.5μm)之Cu基板1(板厚：約0.70mm)上使用遮罩，將焊膏印刷為直徑2.0mm、厚150μm之形狀。接著，將印刷有該焊膏之基板如以下般加熱並接合，製作接合體，以光學顯微鏡確認有於焊料合金粉末未熔融。 As the wettability evaluation 1, as shown in FIG. 2, a mask was used on the Cu substrate 1 (thickness: about 0.70 mm) having a Ni layer 2 (layer thickness: about 2.5 μm), and the solder paste was printed as a diameter. 2.0mm, 150μm thick. Then, the substrate on which the solder paste was printed was heated and joined as follows to prepare a bonded body, and it was confirmed by an optical microscope that the solder alloy powder was not melted.
首先，發動潤濕性試驗機(裝置名：氛圍控制式潤濕性試驗機)，於經加熱之加熱器部分蓋上雙重蓋，並自加熱器部之周圍4個部位流入氮氣(氮氣流量：各12L/分鐘)。隨後，將加熱器設定溫度設定於比各試料熔點高50℃而加熱。加熱器溫度於設定溫度穩定後，將塗佈焊膏之Cu基板設定於加熱器部上，加熱25秒。隨後，自冷卻器部拉起Cu基板，暫時移至整體保持氮氣氛圍之場所予以冷卻。充分冷卻後，取出至大氣中。為了確認焊料合金粉末之未熔融不一定需進行接合體之洗淨等。 First, the wettability tester (device name: atmosphere-controlled wettability tester) was started, and the heated heater was partially covered with a double lid, and nitrogen gas was introduced from four places around the heater portion (nitrogen flow rate: Each 12L/min). Subsequently, the heater set temperature was set to be 50 ° C higher than the melting point of each sample and heated. After the heater temperature was stabilized at the set temperature, the Cu substrate coated with the solder paste was set on the heater portion and heated for 25 seconds. Subsequently, the Cu substrate was pulled up from the cooler portion, and temporarily moved to a place where the nitrogen atmosphere was maintained as a whole to be cooled. After sufficiently cooled, it is taken out to the atmosphere. In order to confirm that the solder alloy powder is not melted, it is not necessary to perform cleaning of the joined body or the like.
如此製作之各接合體以自與焊料合金3所接合之面直 角之方向，即自焊料合金3所接合之面側以光學顯微鏡確認焊料合金粉末有無未熔融。焊料合金粉末殘留時記為「×」，於焊料合金粉末未殘留而焊料合金粉末熔融以具有金屬光澤之焊料合金潤濕擴展於基板上時記為「○」。 Each of the joint bodies thus produced is straight from the surface joined to the solder alloy 3 The direction of the corners, that is, the side of the surface on which the solder alloy 3 was bonded, was confirmed by an optical microscope to check whether or not the solder alloy powder was not melted. When the solder alloy powder remains, it is "x", and when the solder alloy powder does not remain and the solder alloy powder is melted and spread on the substrate by a solder alloy having a metallic luster, it is referred to as "○".
作為潤濕性評價2，以與焊料合金粉末未熔融確認時所製作之接合體同樣製作接合體，該接合體以醇洗淨，隨後真空乾燥，測定於基板上潤濕擴展之焊料合金之縱橫比。針對所得接合體，亦即如圖2所示於Cu基板1之Ni層2上接合有焊料合金3之接合體，求出潤濕擴展之焊料合金3之縱橫比。 As the wettability evaluation 2, a bonded body was produced in the same manner as the bonded body produced when the solder alloy powder was not melted, and the bonded body was washed with an alcohol, followed by vacuum drying to measure the aspect of the wet-extruded solder alloy on the substrate. ratio. With respect to the obtained bonded body, that is, the bonded body of the solder alloy 3 was bonded to the Ni layer 2 of the Cu substrate 1 as shown in FIG. 2, the aspect ratio of the wet-expanded solder alloy 3 was determined.
具體而言，測定圖3所示之最大潤濕擴展長度之長徑(X1)、最小焊料潤濕擴展長度之短徑(X2)，由下述計算式1算出縱橫比。計算式1之縱橫比越接近1越表示基板上潤濕擴展為圓形狀，可判斷為擴展潤濕性良好。隨著大於1，潤濕擴展形狀自圓形偏離，亦即顯示熔融焊料合金之移動距離出現偏差。此種移動距離產生偏差時，合金層厚度或成分之偏差大而成為反應不均一，有無法均一良好地接合之情況。於某方向焊料合金流動較多般擴展時，會有焊料合金量過多之部位與無焊料合金之部位之情況，會因接合不良或因場所而定而無法接合。接合體之縱橫比之測定結果示於表2。 Specifically, the major axis (X1) of the maximum wet spreading length shown in FIG. 3 and the short diameter (X2) of the minimum solder wettability extension length were measured, and the aspect ratio was calculated by the following calculation formula 1. The closer the aspect ratio of the calculation formula 1 is to 1, the wettability on the substrate is expanded to a circular shape, and it can be judged that the expanded wettability is good. As more than 1, the wet spreading shape deviates from the circle, that is, the moving distance of the molten solder alloy is deviated. When such a moving distance is deviated, the thickness of the alloy layer or the variation of the composition is large, and the reaction is not uniform, and it may not be uniformly joined. When the flow of the solder alloy in a certain direction is expanded as much as possible, the portion where the amount of the solder alloy is excessive and the portion where the solder alloy is not present may be bonded due to poor bonding or depending on the location. The measurement results of the aspect ratio of the joined body are shown in Table 2.
[計算式1] 縱橫比=長徑÷短徑=X1÷X2 [Calculation 1] Aspect ratio = long diameter ÷ short diameter = X1 ÷ X2
作為接合性評價1，以與焊料合金粉末未熔融確認時所製作之接合體同樣製作接合體，該接合體以醇洗淨，隨後真空乾燥，關於焊料合金潤濕擴展之接合體如以下般測定孔隙率。 As the bonding property evaluation 1, a bonded body was produced in the same manner as the bonded body produced when the solder alloy powder was not melted, and the bonded body was washed with alcohol, followed by vacuum drying, and the bonded body which was wet-expanded with respect to the solder alloy was measured as follows. Porosity.
針對圖2所示之接合體，使用X射線透過裝置(東芝股份有限公司製，TOSMICRON-6125)測定透過Ni層2接合有焊料合金3之Cu基板1之孔隙率。具體而言，垂直使X射線透過焊料合金3與Cu基板1之接合面自焊料合金3之接合面側，自所得X射線像求出之各面積使用下述計算式2算出孔隙率。接合體之孔隙率之測定結果示於表2。 The porosity of the Cu substrate 1 to which the solder alloy 3 was bonded through the Ni layer 2 was measured by using an X-ray transmission device (TOSMICRON-6125, manufactured by Toshiba Corporation). Specifically, the X-ray is transmitted through the joint surface of the solder alloy 3 and the Cu substrate 1 perpendicularly from the joint surface side of the solder alloy 3, and the porosity is calculated from the respective areas obtained from the obtained X-ray image using the following calculation formula 2. The measurement results of the porosity of the joined body are shown in Table 2.
[計算式2]孔隙率(%)=孔隙面積÷(孔隙面積+焊料合金與Cu基板之接合面積)×100 [Calculation Formula 2] Porosity (%) = Pore Area ÷ (Pore Area + Bonding Area of Solder Alloy and Cu Substrate) × 100
為了確認焊料合金3之接合性，使用焊膏試料如圖4 所示般於Cu基板1(板厚：0.7mm)之Ni層2(層厚：2.5μm)上接合Si晶片4製作接合體，測定剪切強度。以下詳細說明接合體之製作方法及評價方法。 In order to confirm the bondability of the solder alloy 3, a solder paste sample is used as shown in Fig. 4. The Si wafer 4 was bonded to the Ni layer 2 (layer thickness: 2.5 μm) of the Cu substrate 1 (thickness: 0.7 mm) to form a bonded body, and the shear strength was measured. The method of producing the bonded body and the evaluation method will be described in detail below.
接合體之製作係使用黏晶機(Westbond製，型式：3737C)進行。首先事先於Ni層2上將焊膏印刷為2.0mm×2.0mm、厚100μm之形狀，準備Cu基板1。其次於黏晶機之加熱器部邊流入氮氣邊將溫度設為比所使用之焊膏試料之熔點高40℃之溫度後，於加熱器部上載置上述Cu基板1後加熱35秒，於熔融之焊料合金3上載置2.0mm×2.0mm大小之Si晶片4擦洗5秒製作Si晶片接合體。擦洗結束後，快速將接合體移至流動氮氣之冷卻部中，冷卻至室溫後，取出至大氣中。以各焊膏試料進行同樣處理，製作各種Si晶片接合體。其次將製作之接合體固定於剪切強度試驗機上利用治具將Si晶片4自橫方向按壓測定剪切強度。焊料接合體之強度充分高而使晶片破裂時，由於無法測定焊料接合體之剪切強度，故全部稱為「晶片斷裂」。測定結果示於表2。 The production of the joined body was carried out using a die bonder (manufactured by Westbond, type: 3737C). First, the solder paste was printed on the Ni layer 2 in a shape of 2.0 mm × 2.0 mm and a thickness of 100 μm to prepare the Cu substrate 1. Next, the temperature was set to 40 ° C higher than the melting point of the solder paste sample used in the heater portion of the die bonder, and then the Cu substrate 1 was placed on the heater portion and heated for 35 seconds to be melted. The solder alloy 3 was placed on a Si wafer 4 having a size of 2.0 mm × 2.0 mm and rubbed for 5 seconds to prepare an Si wafer bonded body. After the completion of the scrubbing, the joined body was quickly transferred to a cooling portion of flowing nitrogen gas, cooled to room temperature, and taken out to the atmosphere. The same treatment was carried out for each solder paste sample to prepare various Si wafer bonded bodies. Next, the produced bonded body was fixed to a shear strength tester, and the Si wafer 4 was pressed from the lateral direction by a jig to measure the shear strength. When the strength of the solder bonded body is sufficiently high and the wafer is broken, since the shear strength of the solder bonded body cannot be measured, it is referred to as "wafer breakage". The measurement results are shown in Table 2.
為了評價焊料接合體之信賴性而進行熱循環試驗。又，該試驗係使用以與焊料合金粉末未熔融確認時所製作之接合體同樣製作接合體，該接合體以醇洗淨，隨後真空乾燥者進行試驗。試驗首先對於接合體，將-40℃之冷卻與250℃之加熱設為1循環，將其重複特定循環，隨後， 將焊料接合體與Cu基板一起埋入樹脂中，進行剖面研磨，藉由SEM(日立製作所製S-4800)進行接合面觀察。接合面產生剝離、或於焊料合金中產生龜裂時記為「×」，無此等不良，保有與初期狀態同樣之接合面時記為「○」。於300次循環評價為「×」之試料未進行500次循環試驗。結果示於表2。 A thermal cycle test was performed in order to evaluate the reliability of the solder joint. Further, in this test, a joined body was produced in the same manner as the joined body produced when the solder alloy powder was not melted, and the joined body was washed with alcohol and then vacuum dried. The test firstly set the cooling of -40 ° C and the heating of 250 ° C to 1 cycle for the joined body, repeating it for a specific cycle, and then, The solder bonded body and the Cu substrate were embedded in a resin, and subjected to cross-section polishing, and the joint surface was observed by SEM (S-4800, manufactured by Hitachi, Ltd.). When the joint surface is peeled off or cracks occur in the solder alloy, it is indicated as "x", and there is no such defect. When the joint surface similar to the initial state is retained, it is indicated as "○". The sample evaluated as "X" in 300 cycles was not subjected to 500 cycles of testing. The results are shown in Table 2.
(註)表中標註※之試料為比較例。 (Note) The sample marked with * in the table is a comparative example.
如由上述表2所知，本發明之試料1~10之焊 料合金與過去以來之Au系焊料合金之試料15、16同樣，對於各評價項目顯示良好特性。亦即，關於潤濕性評價1的焊料合金粉末之未熔融，全部都熔融。關於潤濕性之評價2的縱橫比測定結果，均一潤濕擴展為縱橫比1.03以下之圓形狀。關於接合性之評價1的孔隙率測定結果，獲得孔隙率0.4%以下之良好結果。關於潤濕性之評價2的剪切強度之測定結果，焊料合金之強度高，全部晶片斷裂，焊料合金中均無破壞。關於信賴性評價的熱循環試驗，於500次循環之前並未發生不良。 As is known from the above Table 2, the welding of the samples 1 to 10 of the present invention In the same manner as the samples 15 and 16 of the conventional Au-based solder alloy, the alloy showed good characteristics for each evaluation item. That is, all of the solder alloy powders of the wettability evaluation 1 were not melted, and all of them were melted. As a result of the aspect ratio measurement of the wettability evaluation 2, the uniform wetting spread was a circular shape having an aspect ratio of 1.03 or less. As a result of measuring the porosity of the evaluation 1 of the bondability, a good result of a porosity of 0.4% or less was obtained. As a result of measuring the shear strength of the wettability evaluation 2, the strength of the solder alloy was high, and all the wafers were broken, and there was no damage in the solder alloy. Regarding the thermal cycle test of the reliability evaluation, no failure occurred before 500 cycles.
如此，藉由使用適當組成範圍內之焊料合金，以適當條件製造本發明之焊膏，可獲得良好結果。 Thus, good results can be obtained by using the solder alloy in an appropriate composition range to produce the solder paste of the present invention under appropriate conditions.
另一方面，比較例的試料11~14之各焊料合金，各特性為不佳之結果。亦即，試料11~14發生焊料合金粉末之未熔融，縱橫比為1.30以上。進而有關剪切試驗，試料11~14中晶片未斷裂，剪切強度為38~53MPa之較低值。關於孔隙率，有孔隙以相當於10~23%左右之比例發生之情況。而且於信賴性評價之熱循環試驗中，關於試料11~14全部試料在300次循環之前即發生不良。 On the other hand, in each of the solder alloys of the samples 11 to 14 of the comparative example, the respective characteristics were inferior. That is, the solder alloy powder was not melted in the samples 11 to 14, and the aspect ratio was 1.30 or more. Further, regarding the shear test, the wafers in the samples 11 to 14 were not broken, and the shear strength was a low value of 38 to 53 MPa. Regarding the porosity, there is a case where the pores occur in a ratio equivalent to about 10 to 23%. Further, in the heat cycle test of the reliability evaluation, all the samples of the samples 11 to 14 were inferior before 300 cycles.
本發明使用之焊料合金即使Au含量較多而為48%左右，Au含量亦比目前實用化之80質量%Au-20質量%合金或87.5質量%Au-12.5質量%Ge合金等更格外地少，因此可知為非常低成本。 The solder alloy used in the present invention is about 48% even if the Au content is large, and the Au content is more exceptionally less than the currently practical 80% by mass of the Au-20% by mass alloy or the 87.5% by mass of the Au-12.5 mass% Ge alloy. Therefore, it can be known that it is very low cost.
如以上所述，本發明之焊膏顯示與以往之Au系焊料同樣之特性同時可實現低成本。 As described above, the solder paste of the present invention exhibits the same characteristics as the conventional Au-based solder and at the same time achieves low cost.
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