TW201622867A - 焊接材料、焊接接頭以及焊接材料之製造方法 - Google Patents

焊接材料、焊接接頭以及焊接材料之製造方法 Download PDF

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Publication number
TW201622867A
TW201622867A TW104128294A TW104128294A TW201622867A TW 201622867 A TW201622867 A TW 201622867A TW 104128294 A TW104128294 A TW 104128294A TW 104128294 A TW104128294 A TW 104128294A TW 201622867 A TW201622867 A TW 201622867A
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Taiwan
Prior art keywords
solder
less
layer
sno
film
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TW104128294A
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English (en)
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TWI543835B (zh
Inventor
Hiroyoshi Kawasaki
Takahiro Roppongi
Daisuke Soma
Isamu Sato
Yuji Kawamata
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Senju Metal Industry Co
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Publication of TWI543835B publication Critical patent/TWI543835B/zh

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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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • 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
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • 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
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
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    • C23C8/10—Oxidising
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract

本發明提供可抑制氧化膜成長的焊接材料。焊接材料之焊球1A由焊接層2、覆蓋焊接層2的覆蓋層3所構成。焊接層2為球狀，且由Sn含量40%以上的合金構成。或是，焊接層2由Sn含量為100%的金屬材料構成。覆蓋層3可在焊接層2的外側形成SnO膜3a，且在SnO膜3a的外側形成SnO2膜3b。覆蓋膜3的厚度為大於0nm、4.5nm以下較佳。再者，焊球1A的黃色度為5.7以下較佳。

Description

焊接材料、焊接接頭以及焊接材料之製造方法
本發明為有關於以Sn作為主成分的焊接材料、焊接接頭以及焊接材料的製造方法。
近年來，由於小型情報機器的發達，其所搭載的電子元件急速地小型化正進行著。電子元件為了小型化的需求，而對應連接端子的窄小化或封裝面積的縮小化，可適用背面設置著電極的球柵陣列(ball grid array，以下稱為「BGA」)。
適用BGA的電子元件例如有半導體封裝。半導體封裝為將含有電極的半導體晶片以樹脂密封。在半導體晶片的電極上，形成焊料凸塊。此焊料凸塊可藉由將焊球接合於半導體晶片的電極而形成。適用BGA的半導體封裝置於印刷電路板上，使得各焊料凸塊與印刷電路板的導電性連接盤(land)接觸，藉由加熱而熔融的焊料凸塊與連接盤接合，而搭載於印刷電路板。
那麼，為了將焊球接合於電極，需要抑制焊球的表面形成金屬氧化膜。再者，混合焊球與助焊劑(flux)，而作為焊膏(solder paste)使用時，需要抑制保存時的黏度上昇。
在此，焊球表面上形成的氧化膜的膜厚與黃色度有比例關係。於是，使用黃色度在預定值以下，亦即，使用氧 化膜在預定值以下的焊球，藉由加熱破壞氧化膜使焊球能結合的技術(例如，參照專利文獻1)被提出。此專利文獻1中揭示：首先，挑選在製造後表面的黃化度成為10以下的焊球，藉由嚴密地管理保存狀態而防止焊球表面的黃化，即，抑制焊球表面的SnO氧化膜成長的同時，使用此焊球形成的焊料凸塊之表面，形成SnO氧化膜以及SnO2氧化膜。
再者，在焊球的表面上形成預定值的氧化膜，並可抑制黏度上昇的技術(例如，參照專利文獻2)被提出。此專利文獻2中揭示：可抑制在焊接粒子表面形成以SnO或SnO2為主成分之氧化錫構成的氧化覆膜，且與助焊劑混合．攪拌而製造的焊膏製造後經過時間造成的黏度上昇。
先前技術文獻 專利文獻
專利文獻1：特開2009-248156號公報
專利文獻2：特許第4084657號公報
以Sn作為主成分的焊球，其Sn與空氣中的O2反應而形成SnO膜。此膜厚增加時，焊接時助焊劑的除去變得困難，焊球的表面上殘留氧化膜時，潤濕性變差。再者，一旦氧化膜厚增加時，黃色度上昇。有時利用黃色度作為焊球的外觀檢查，若不能抑制氧化膜厚的增加，焊球被判斷為不適合使用的可能性變高。
專利文獻1因為嚴密地管理保存狀態，可抑制焊球表面的SnO氧化膜的成長。再者，專利文獻1著眼於結晶質的SnO2氧化膜，因伴隨焊球的溶融之內部變形而容易破損，使焊料與電極端子的接合性改善，但在保存狀態的管理以外，完全沒有揭示以氧化膜的組成而抑制氧化膜的成長。更進一步地說，關於專利文獻2，完全沒有揭示關於抑制SnO氧化膜的成長。
於是，本發明可抑制氧化膜的成長，並因此，提供保存性及潤濕性良好的焊接材料，焊接接頭及焊接材料的製造方法為目的。
本發明者們發現以Sn為主成分的焊接層，藉由覆蓋含有SnO及SnO2的覆蓋層，可抑制氧化膜的成長。又，含有SnO及SnO2的覆蓋層係表示以SnO為主成分的由氧化錫構成之氧化覆膜層，以及，以SnO2為主成分的由氧化錫構成之氧化覆膜層。在以下的說明中也一樣。
申請專利範圍第1項記載的發明為一種焊接材料，其包括：焊接層，由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成；以及覆蓋層，覆蓋上述焊接層表面之直徑1~1000μm的球體，覆蓋層為在上述焊接層的外側形成SnO膜、在SnO膜的外側形成SnO2膜，覆蓋層的厚度為大於0nm、4.5nm以下。
申請專利範圍第2項所述之發明為，如申請專利範圍第1項所述之焊接材料中，在L*a*b*表色系統中的黃色 度為5.7以下。
申請專利範圍第3項記載的發明為一種焊接材料，包括：焊接層，由Sn的含量為40%以上的合金所構成的金屬材料或由Sn的含量為100%的金屬材料所構成的；以及覆蓋層，覆蓋焊接層表面之直徑1~1000μm的球體，覆蓋層為在焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜，且該焊接材料的L*a*b*表色系統中的黃色度為5.7以下。
申請專利範圍第4項記載的發明為，如申請專利範圍第1~3項中任一項所述之焊接材料，其中焊接層含有Ag為0%以上、小於4%，Cu為0%以上、小於1%、P為0ppm以上、小於5ppm、Ge為0ppm以上、小於20ppm。
申請專利範圍第5項記載的發明為，如申請專利範圍第1~4項中任一項所述之焊接材料，其中焊接層使Sn含量成為40%以上，(i)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為1%以下或者是各別元素為小於1%，以及，從In、Bi選擇至少一個以上元素，使其含有整體為40%以下，或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%，或者是：(ii)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%，或者是各別元素為小於1%，或是，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%。
申請專利範圍第6項記載的發明為，申請專利範圍第1~5項中任一項所述之焊接材料，其中放射的α線量為 0.0200cph/cm2以下。
申請專利範圍第7項記載的發明為，一種焊接接頭，其特徵在於使用如申請專利範圍第1~6項中任一項所述之焊接材料而得到。
申請專利範圍第8項記載的發明為，一種焊接材料的製造方法，其特徵在於包括：由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成的焊接層之焊接層的形成步驟；以及在上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜之包含厚度大於0nm、4.5nm以下的覆蓋層形成於焊接層的表面的氧化膜的形成步驟，以製造直徑為1~1000μm的球體。
申請專利範圍第9項記載的發明為，如申請專利範圍第8項所述之焊接材料的製造方法，其中在上述氧化膜形成步驟，形成覆蓋層表面的L*a*b*表色系統中黃色度為5.7以下。
申請專利範圍第7項記載的發明為，如申請專利範圍第8項或第9項所述之焊接材料的製造方法，其中在上述氧化膜的形成步驟，照射O2-Ar電漿(plasma)於上述焊接層的表面。
於本發明，將焊接層覆蓋的覆蓋層中，在SnO膜的外側形成SnO2膜時，可抑制Sn與空氣中的O2的反應，而抑制SnO膜及SnO2膜的成長，可抑制膜厚的增加，再者，藉由抑制膜厚的增加，可抑制黃變，並可抑制L*a*b*表色系統 中的黃色度在5.7以下。因此，能提供保存性及潤濕性良好的焊接材料，以及，使用此焊接材料的焊接接頭。
1A‧‧‧焊球
2‧‧‧焊接層
3‧‧‧覆蓋層
3a‧‧‧SnO膜
3b‧‧‧SnO2膜
第1圖為顯示作為本實施形態的焊接材料之一例的焊球的示意構造的剖面圖。
第2A圖為顯示作為本實施形態的焊接材料之一例的焊球製造方法的示意剖面圖。
第2B圖為顯示作為本實施形態的焊接材料之一例的焊球製造方法的示意剖面圖。
第2C圖為顯示作為本實施形態的焊接材料之一例的焊球製造方法的示意剖面圖。
以下對於本發明的焊接材料、焊接接頭及焊接材料的製造方法進行說明。
〈焊接材料的構成例〉
第1圖為顯示作為本實施形態的焊接材料之一例的焊球示意剖面圖。又，在本說明書中，關於焊接材料的組成之單位(ppm及ppb)若並無特別指定時表示對質量的比例(質量ppm、質量ppb及質量%)。
本實施形態的焊球1A由焊接層2以及覆蓋焊接層2的覆蓋層3構成。焊接層2為球狀，且由0%以上、小於4%的Ag、0%以上、小於1%的Cu、Sn含量40%以上的合金構成。通常，雖然添加了預定量的P或Ge而增進了抗氧化性，但在 本發明中不添加這些也可增進抗氧化性。不過，在本發明中即使添加小於5ppm的P，添加小於20ppm的Ge，也不會損及本發明的效果。因此，即使不添加P或Ge也可以，若要添加的話，使P的添加量在小於5ppm，Ge的添加量為小於20ppm，所以，使P的添加量在0ppm以上、小於5ppm，Ge的添加量在0ppm以上、小於20ppm。
再者，焊接層2為使Sn的含量成為40%以上的方式，從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%，或者是各別元素為小於1%，以及，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%，或是In、Bi其中一個元素為小於40%，另一個元素為小於20%。
或者是，從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%或各別元素為小於1%，或是，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%，或是In、Bi其中一個元素為小於40%，另一個元素為小於20%。
更進一步地，焊接層2由Sn含量為100%的金屬材料構成也可以，又，以從焊接層2放射的α射線量在0.0200cph/cm2以下的材料較佳。
覆蓋層3為，在焊接層2的外側形成SnO膜3a，並在SnO膜3a的外側形成SnO2膜3b。焊球1A因接觸空氣，在焊球層2的表面形成的SnO層將隨著時間的經過而變厚。再者，若膜厚變厚，焊球1A的表面將發生黃變。
相對於此，若在焊接層2的外側形成SnO膜3a， Sn與空氣中的O2的反應受到抑制，並且SnO膜3a及SnO2膜3b本身的成長也受到抑制的關係，造成膜厚的增加受到了抑制的結果。再者，因為膜厚的增加受到抑制，黃變受到抑制，使得構成焊接層2的金屬材料可保持既有的銀白色。
焊球1A以1~1000μm直徑較佳，再者，覆蓋層3的厚度以大於0nm(表示不包含0nm)、4.5nm以下較佳。覆蓋層3的厚度若超過4.5nm，焊接時以助焊劑進行覆蓋層3的去除變得困難，而使濕潤性變差。
再者焊球1A的黃色度b*以5.7以下較佳，在管理製造、保存焊球1A時，會有利用黃色度的情形。這是因為所謂黃色度高，表示SnO的膜厚較厚，黃色度超過既定值的焊球，會被當作不適合使用者而可以排除。
亮度及黃色度以使用KONICA MINOLTA製CM-3500d2600d型分光光度計，以D65光源、10度的視野並以JIS Z 8722「顏色的測定方法-反射及透射物體」為準則測定分光穿透率，從色彩值(L*、a*、b*)而求得。
又，色彩值(L*、a*、b*)為如同JIS Z 8729「顏色的表示方法-L*a*b*表色系統及L*U*V*表色系統」中的規定。
又，焊接材料的形狀雖然在本例為球狀，然而也可以為圓筒狀、四角柱狀等其他的形狀。再者，從焊球1A放射的α射線也以在0.0200cph/cm2以下者較佳。
〈焊接材料的製造方法例〉
第2A圖、第2B圖及第2C圖為表示作為本實施形態的焊接材料之一例的焊球的製造方法的示意剖面圖。
形成焊接層的步驟如第2A圖所示，以上述從Sn含量40%以上的合金構成的金屬材料，或是以Sn含量為100%的金屬材料，形成球狀的焊接層2。形成焊接層的步驟在本例中使用將熔融的金屬材料滴下硬化成為球狀的滴下法。
形成氧化膜的步驟，如第2B圖所示，在焊接層2的表面因接觸空氣產生的SnO膜3a，如第2C圖所示，形成SnO2膜3b。氧化膜形成的方法，可使用一般已知的方法。例如，可列舉氣相沈積法、濺鍍法、電漿照射法等方法。在本例中，形成氧化膜的步驟，使用已知的大氣電漿裝置以電漿照射法實施，電漿照射法係將熔融金屬從滴下至硬化的期間，以高濃度的O2-Ar電漿照射。
根據以上的製造方法，可製造在含有既定直徑的焊接層2的表面，形成有覆蓋層3的焊球1A。覆蓋層3a為厚度大於0nm、4.5nm以下，且在焊接層2的外側形成SnO膜3a、SnO膜3a的外側形成SnO2膜3b。再者，焊球的黃色度為5.66以下。
〈實施例〉
以Ag 3%、Cu 0.5%，剩餘部份由Sn構成的金屬材料，根據滴下法製造相當於焊接層2的金屬球，此金屬球以電漿照射法形成相當於覆蓋層3的覆膜，生成實施例的焊球。電漿照射法為熔融的金屬材料至滴下的期間，照射高濃度的O2-Ar電漿。
在表面以自然氧化形成SnO層而生成焊球，作為比較例。
實施例與比較例的焊球以200℃加熱，以黃色度 b*的值，觀察氧化行為的結果如表1所示。
如表1所示，相對於比較例的焊球快速上升的黃色度b*的值，實施例的焊球根據連續電化學還原法(SERA，Sequential Electrochemical Reduction Analysis)的定性分析，可得知藉由以Sn作為主成份的焊接層的外側形成SnO層、SnO層的外側形成SnO2層，可抑制氧化膜厚的成長。
再者，為了作為參考，比較例中因分離氧化步驟與加熱試驗步驟，在200℃進行1分鐘的加熱，之後，冷卻後進行再度加熱，但與步驟分離前同樣地，黃色度b*的值快速地上升。
接著，上述實施例的焊球，利用FE-AES(場發射式歐傑電子光譜)定量分析在200℃進行15分加熱的實施例1的焊球與在200℃進行30分鐘加熱的實施例2的焊球的氧化膜厚，並且根據連續電化學還原法(SERA，sequential electrochemical reduction analysis)進行定性分析，確認形成的氧化膜成分為Sn的氧化物(SnO及SnO2)。
並且，以FE-AES實施定量分析的方式，因為SERA的分析數值容易分散，雖然定性分析是可能的，但作為可具體定量分析氧化膜厚之討論而言，還是以FE-AES分析的方式，容易顯示固定值。氧化膜的膜厚是以下的裝置及條件測定。並且，氧化膜厚的測定值為依據SiO2換算求得。
測定裝置：ULVAC-PHI，INC製，掃瞄型FE歐傑電子分光分析裝置。
測定條件：Beam Voltage：10kV，樣品電流：10nA(使用Ar離子槍的濺鍍深度的測定方法，以ISO/TR 15969為準則)。
表2顯示氧化膜厚和黃色度的測定結果。
如表2所示，可知氧化膜厚抑制至5nm以下，覆蓋層的膜厚可知較佳為4.5nm以下。再者，可知黃色度抑制在10以下，從表2的結果來看，可知5.7以下較佳。
其次，以上述的實施例和比較例的焊球，製造膜厚、黃色度的變更品，檢驗保存性和濕潤性。
各實施例的焊球，膜厚為4.5nm以下，實施例1的焊球，膜厚為2.6nm，實施例2的焊球，膜厚為4.1nm，實施例3的焊球，膜厚為1.5nm。
再者，各實施例的焊球，黃色度為5.7以下，實施例1的焊球，黃色度為4.60，實施例2的焊球，黃色度為5.77，實施例3的焊球，黃色度為3.90。
另一方面，各比較例的焊球，膜厚為10nm以上，再者，黃色度為10以下，比較例1的焊球，黃色度為10.21，比較例2的焊球，黃色度為13.15。
檢驗結果顯示於表3
如表3所示，實施例1至實施例3的焊球，不論哪一個的保存性及濕潤性都滿足既定的條件，另一方面，各比較例的焊球，不論是保存性或是濕潤性，都不能滿足既定的條件。
因此，可知覆蓋層的厚度大於0nm、4.5nm以下，黃色度b*為5.7以下的焊球，無論保存性及濕潤性都提升。
並且，關於本發明的焊接材料，能夠以焊膏電性接合於電極，可使用於電子元件的焊接接頭。
1A‧‧‧焊球
2‧‧‧焊接層
3‧‧‧覆蓋層
3a‧‧‧SnO膜
3b‧‧‧SnO2膜

Claims (10)

  1. 一種焊接材料，其特徵為包括：焊接層，由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成；以及覆蓋層，覆蓋上述焊接層表面之直徑1~1000μm的球體，上述覆蓋層為在上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜，上述覆蓋層的厚度為大於Onm、4.5nm以下。
  2. 如申請專利範圍第1項所述之焊接材料，其中在L*a*b*表色系統中的黃色度為5.7以下。
  3. 一種焊接材料，其特徵為包括：焊接層，由Sn的含量為40%以上的合金所構成的金屬材料或由Sn的含量為100%的金屬材料所構成的；以及覆蓋層，覆蓋上述焊接層表面之直徑1~1000μm的球體，上述覆蓋層為上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜；該焊接材料的L*a*b*表色系統中的黃色度為5.7以下。
  4. 如申請專利範圍第1~3項中任一項所述之焊接材料，其中上述焊接層含有Ag為0%以上、小於4%，Cu為0%以上、小於1%、P為0ppm以上、小於5ppm、Ge為0ppm以上、小於20ppm。
  5. 如申請專利範圍第1~4項中任一項所述之焊接材料，其中上述焊接層以使Sn含量成為40%以上的方式，(i)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有 整體為1%以下或者是各別元素為小於1%，以及，從In、Bi選擇至少一個以上元素，使其含有整體為40%以下，或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%，或者是：(ii)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%，或者是各別元素為小於1%，或是，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%。
  6. 如申請專利範圍第1~5項中任一項所述之焊接材料，其中放射的α線量為0.0200cph/cm2以下。
  7. 一種焊接接頭，其特徵在於使用如申請專利範圍第1~6項中任一項所述之焊接材料而得到。
  8. 一種焊接材料的製造方法，其特徵在於包括：由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成的焊接層之焊接層的形成步驟；在上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜之厚度大於0nm、4.5nm以下的覆蓋層形成於上述焊接層的表面的氧化膜形成步驟以製造直徑為1~1000μm的球體。
  9. 如申請專利範圍第8項所述之焊接材料的製造方法，其中在上述氧化膜形成步驟，形成上述覆蓋層表面的L*a*b*表色系統中黃色度為5.7以下。
  10. 如申請專利範圍第8項或第9項所述之焊接材料的製造方 法，其中在上述氧化膜的形成步驟，照射O2-Ar電漿於上述焊接層的表面。
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