TW202026086A - 焊接球、焊接接頭及接合方法 - Google Patents

焊接球、焊接接頭及接合方法 Download PDF

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TW202026086A
TW202026086A TW108140222A TW108140222A TW202026086A TW 202026086 A TW202026086 A TW 202026086A TW 108140222 A TW108140222 A TW 108140222A TW 108140222 A TW108140222 A TW 108140222A TW 202026086 A TW202026086 A TW 202026086A
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Taiwan
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mass
solder
solder ball
ball
concentration
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TW108140222A
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English (en)
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TWI696515B (zh
Inventor
川浩由
中村優里
宗形修
鶴田加一
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日商千住金屬工業股份有限公司
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    • 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
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • 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
    • B23K3/00—Tools, devices, or special appurtenances for soldering, e.g. brazing, or unsoldering, not specially adapted for particular methods
    • B23K3/06—Solder feeding devices; Solder melting pans
    • B23K3/0607—Solder feeding devices
    • B23K3/0623—Solder feeding devices for shaped solder piece feeding, e.g. preforms, bumps, balls, pellets, droplets
    • 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
    • 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
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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    • H01L23/00—Details of semiconductor or other solid state devices
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    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B23K2101/36—Electric or electronic devices
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Abstract

本發明提供一種焊接球，In為0.1質量%以上10質量%以下，添加 Ag：0以上4質量%以下， Cu：0以上1.0質量%以下， 選自Bi、Sb的群組合計為0~3質量%， 選自Ni、Co、Fe、Ge、P的群組合計為0~0.1質量% 當中的至少1種以上的元素， 餘份為Sn， 在L*a*b*表色系中的黃色度(b*)為2.8以上15.0以下， L*a*b*表色系中的明度(L*)為60以上100以下。

Description

焊接球、焊接接頭及接合方法
本發明是關於一種焊接球、焊接接頭以及接合方法。
隨著近來的電子組件的小型化、高密度組裝化，在將電子組件組裝於印刷配線基板等時，可使用BGA(Ball Grid Array)、CSP(Chip Size Package)技術。作為電子組件的焊附中所使用的焊料合金的組成，可列舉，Sn-In系的無鉛焊料。已知Sn-In系的無鉛焊料，藉由在Sn中添加特定量的In，達到各種效果。
例如，在對於依序實施Ni、Au的處理的Cu電極的表面進行焊附時，在Sn中的Au的擴散速度極快，由於Au在Sn中的擴散，使得Au鍍覆在電極上消失，而有Au的基底層的Ni、Cu與無鉛焊料的Sn間的IMC的成長容易促長的問題。此外，無鉛焊料的濕潤性會有低下的問題。因此，例如，在非專利文獻1中，揭示一種藉由使用使In的含量增加的Sn-In系的無鉛焊料，延遲In在Sn中的擴散速度的技術。 [先前技術文獻] [非專利文獻]
非專利文獻1：宗司郁夫著「在Au與In-Sn系焊料的界面上介金屬化合物成長過程」光電組裝學會期刊、1999年、p.121-126
[發明欲解決的問題]
然而，在Sn-In系的無鉛焊料中，使In的添加量增加，會有因作為稀有金屬的In量的增加而造成成本上升，同時作為低溫焊料的Sn-In的焊料使焊料熔點劇烈降低的問題。因此，期望藉由一定量的In的添加，能夠更加發揮In的添加所帶來的效果的Sn-In系無鉛焊料材料。
因此，本發明為鑒於上述課題而完成者，其目的為提供一種在Sn-In系焊料中，不增加In的添加量，仍可確保在焊接時焊料的濕潤性的焊接球、焊接接頭以及接合方法。 [解決問題的手段]
為了解決上述課題，本發明者等發現，改良既有的Sn-In系的無鉛焊料合金，在將Sn-In系的無鉛焊料合金加工成球狀的焊接球中，在接合焊接球前的階段，對焊接球本身實施進行加熱等的熟成(aging)處理，藉由在焊接球表面形成使In濃化(concentration)的氧化膜，能夠抑制在焊接時Au在焊料中的擴散。
本發明為如以下者。 (1)一種焊接球，其In為0.1質量%以上10質量%以下，餘份為Sn，在L*a*b*表色系中的黃色度(b*)為2.8以上15.0以下，在L*a*b*表色系中的明度(L*)為60以上100以下。
(2)如上述(1)所記載之焊接球，其中，In為0.1質量%以上7質量%以下。
(3)如上述(1)或(2)所記載之焊接球，其中，球徑為0.1μm以上120μm以下。
(4)如上述(1)至(3)中任一項所記載之焊接球，其中，添加Ag：0以上4質量%以下，Cu：0以上1.0質量%以下，選自Bi、Sb的群組者合計為0~3質量%，選自Ni、Co、Fe、Ge、P的群組合計為0~0.1質量%，當中至少1種以上的元素(惟，由Ag：3質量%，Cu：0.5質量%，In：0.2質量%，餘份為Sn所構成之焊接球除外)。
(5)一種焊接接頭，使用上述(1)至(4)中任一項所記載之焊接球。
(6)一種接合方法，具有：將上述(1)至(4)中任一項所記載之複數個焊接球配置在電極上的步驟；將配置在上述電極上的上述複數個焊接球使用有機酸氣體進行熔融的步驟。 [發明的效果]
根據本發明，即使面對使用Sn-In系的無鉛焊料時所發生的問題，仍可防止In的添加量增加，並且藉由抑制在焊接時Au在焊料中的擴散，而無損焊料的濕潤性的同時抑制IMC的成長。
本實施形態相關的焊接球，以Sn作為主成分，含有In超過0質量%10質量%以下，在L*a*b*表色系中的黃色度(b*)為2.8以上15.0以下。焊接球在L*a*b*表色系中的明度(L*)為60以上100以下，焊接球的球徑為0.1μm以上120μm以下。此外，本實施形態相關的焊接球，在其表面具有特定厚度所形成的氧化膜。氧化膜為藉由實施熟成處理而形成。作為熟成處理，可列舉，例如，大氣暴露(放置)、加熱處理。
(1)In：超過0質量%且10.0質量%以下 焊接球中的In的含量，超過0質量%且10.0質量%以下。由於In的含量超過0質量%，藉由能夠確保In有一定量，可防止Au在焊料中的擴散。此外，由於In的含量10.0質量%以下，藉由氧化膜的成長可抑制在一定的範圍，不會使焊料的濕潤性降低，可防止Au在焊料中的擴散。再者，藉由In的含量為上述範圍，由於能夠減少In的含量，可謀求低成本。此外，作為In的含量的較佳範圍，為超過0.1質量%7.0質量%以下，作為更佳範圍，為3.0質量%以上7.0質量%以下。且，In的上述含量，為藉由熟成處理所引起In的濃化而實現。
(2)焊接球的球徑：0.1μm以上120μm以下 焊接球的球徑為0.1μm以上120μm以下。焊接球的球徑超過120μm時，在精細節距(fine pitch)進行焊附變得困難，無法符合基板的微小化、電子組件的電極的窄間距化的要求。關於下限值，作為技術上在焊料隆點形成用能夠使用的球徑的界限，為0.1μm以上。如此一來，藉由焊接球10的球徑成為0.1μm以上120μm以下的範圍，變得可對應電子組件的小型化、高積體化。再者，上述Au在焊料中的擴散防止效果，因為焊接球的粒徑縮小而獲得發揮。因此，焊接球的球徑以120μm以下為佳，以80μm以下為更佳，再者以50μm以下為佳，進一步更佳為30μm以下。
(3)在L*a*b*表色系中的黃色度(b*)：2.8以上15.0以下 焊接球在L*a*b*表色系中的黃色度(b*)為2.8以上15.0以下。若黃色度(b*)為2.8以上15.0以下的範圍，變得可有效抑制在焊接時Au在焊料中的擴散。焊接球在預定溫度以預定時間進行熟成處理時，在焊接球的表面形成含有多量的氧化銦(InO)的氧化膜，焊接球的表面的In的濃度變高而發生濃化現象。如本實施形態，即使當In的含量為超過0質量%10.0質量%的低濃度時，藉由有意地使焊接球表面氧化，因為能夠使焊接球表面的In高濃度化，可獲得抑制Au在焊料中的擴散的效果。在此，推測使焊接球過度地氧化而使焊接球表面的In的濃度變高時，可更加提高Au在焊料中的擴散抑制效果。但是，球徑為120μm以下的焊接球，由於氧化膜的影響變得特別大，而有使焊接時的可靠性降低的問題。因此，滿足考慮焊附性的氧化膜厚以及考慮In濃化引起的Au在焊料中的擴散抑制效果的氧化膜厚兩者的條件的氧化膜厚的管理變成必要。因此，本實施形態為了簡易且迅速的管理形成在焊接球的表面的氧化膜厚，而採用L*a*b*表色系中的黃色度(b*)，藉由製作成為L*a*b*表色系中的黃色度(b*)為2.8以上15.0以下的焊接球，而實現特定氧化膜厚的焊接球。黃色度(b*)未達2.8時，In未被濃化，有時在焊料隆點形成時無法有效地抑制Au在焊料中的擴散。相對於此，黃色度(b*)超過15.0時，會損害焊接球接合時的焊料的濕潤性，同時焊料材的成本會上升。且，黃色度(b*)更佳為7以下。
(4)在L*a*b*表色系中的明度(L*)：60以上100以下 當焊接球藉由熟成處理使氧化膜變厚時，具有在L*a*b*表色系中的黃色度(b*)會上升，另一方面，在L*a*b*表色系中的明度(L*)會下降的相關關係。因此，作為根據焊接球的熟成處理的氧化膜厚的管理方法，上述在L*a*b*表色系中的黃色度(b*)外，在L*a*b*表色系中的明度(L*)也可作為管理氧化膜的指標之一使用。焊接球在L*a*b*表色系中的明度(L*)為60以上100以下。明度(L*)未達60時，In未被濃化，有時在焊料隆點形成時無法有效的抑制Au在焊料中的擴散。相對於此，明度(L*)超過100時，有時會損害焊接球接合時的焊料的濕潤性。且，明度(L*)的上限值更佳為80以下。
(5)添加Ag：0以上4質量%以下，Cu：0以上1.0質量%以下，選自Bi、Sb的群組合計為0以上3質量%以下，選自Ni、Co、Fe、Ge、P的群組合計為0以上0.1質量%以下，當中的至少1種以上的元素 構成本發明的焊接球以上述範圍含有Ag、Cu、Bi、In、Sb、Ni、Co、Fe、Ge、P。如此一來，可圖求接合可靠性的提升。Ag、Cu、Bi、In、Ni、Sb、Co、Fe、Ge、P的含量，為了不妨礙In與接合構件間的反應，以Ag：0以上4質量%以下，Cu：0以上1.0質量%以下，選自Bi、In、Sb的群合計為0以上3質量%以下，選自Ni、Co、Fe、Ge、P的群組合計為0以上0.1質量%以下為佳。
(6)餘份：Sn 本發明相關的焊接球的餘份為Sn。亦即，焊接球的主成分為Sn，在焊接球中的金屬元素當中經常成為最多含量者。亦可含有上述元素之外無法避免的雜質。即使是含有無法避免的雜質，並不影響上述效果。此外，本發明中不包含的元素即使作為無法避免的雜質而含有，也不影響上述的效果。
(7)α射線量：0.0200cph/cm2 以下 本發明相關的焊接球的α射線量，從抑制軟誤差(soft error)的觀點而言，為0.0200cph/cm2 以下。此為在電子組件的高密度組裝中，軟誤差不會成為問題的程度的α射線量。α射線量，從抑制在更加高密度組裝的軟誤差的觀點而言，更佳為0.0010cph/cm2 以下。
(8)焊接球的製造方法 首先，球徑為0.1μm以上120μm以下，製作含有In超過0且10.0質量%以下的焊接球。作為焊接球的製作方法，可採用使熔融的焊料滴下後加工成球狀的滴下法、氣體霧化法等的習知方法。焊接球中可添加1種或2種以上選自Ag、Cu、Bi、Ni、Sb、Co、Fe、Ge、P所構成的群的元素。
接著，藉由將所製作的焊接球進行熟成處理而在焊接球表面形成氧化膜，以使焊接球的表面的In的濃度變高的方式進行控制。熟成處理以形成焊接球的黃色度(b*)成為2.8以上15.0以下的氧化膜厚的方式，設定加熱溫度以及加熱時間。此外，作為其他使In的濃度變高的方式進行控制的方法，有室溫下在大氣暴露長時間保存，藉由造球時的氧濃度增大而熟成，造球時或造球後的至少任一者實施氧電漿照射等。如此一來，可製造在表面形成有由一定厚度所構成的氧化膜的焊接球。
根據本實施形態相關的焊接球，例如，即使在含Au的電極上使用焊接球時，In的添加量不增加，藉由形成在焊接球表面的氧化膜可抑制Au在焊料中的擴散，可防止焊接時的焊料的濕潤性的降低。此外，由於可壓抑在Sn中In的添加量，可防止焊料熔點劇烈地降低。
且，本發明相關的焊接球，也可使用在電極間進行接合的焊接接頭的形成。本發明，例如，將焊料隆點安裝在印刷基板的電極上的構造稱為焊接接頭。所謂焊料隆點，例如，是指在半導體晶片的電極上安裝焊接球的構造。
此外，本發明相關的焊接球，也適用在不使用助焊劑進行接合的接合方法中。例如，熟成處理進行後複數個焊接球載置(配置)在基板的電極上後，將所載置的複數個焊接球，使用有機酸氣體進行熔融，而形成焊料隆點。且，焊接球使用50個焊接球的直徑的測定值的算術平均成為120μm者。即使此時，仍有效的抑制Au在焊料中的擴散。 [實施例]
首先，製作球徑為120μm，依各實施例所示的合金組成的Sn-In的焊接球。接著，所製作的各焊接球分別在相異條件下預先實施熟成處理，處理焊接球的表面使其氧化，藉由使其表面的In的濃度提高，製作形成有含有高濃度的氧化銦，例如In2 O3 等的氧化膜的焊接球。接著，在各焊接球上，分別測定黃色度(b*)、明度(L*)以及焊接球表面的In的濃度。
(1)焊接球的黃色度(b*)以及明度(L*)的測定 焊接球的黃色度(b*)以及明度(L*)，使用KONICA MINOLTA, INC.製CM-2600d型分光色度計進行測定。
(2)焊接球表面的In的濃度的測定 焊接球的表面的In的濃度，以場發射型電子射線微量分析儀(Field Emission Electron Probe MicroAnalyser： FE-EPMA)進行定性分析，引用半定量分析值。且，焊接球表面的In的濃度為了比較濃度變化，計算出半定量分析值。
(3)焊接球表面的In的濃度的評價 準備未進行熟成處理的Sn-In的焊接球，藉由將此焊接球的半定量分析值作為基準與進行熟成處理的各焊接球中的In的半定量分析值進行比較，進行In的濃化的評價。 (a)實施例或比較例的焊接球的半定量分析值超過基準的焊接球的半定量分析值時：○(濃化大) (b)實施例或比較例的焊接球的半定量分析值為基準的焊接球的半定量分析值以下時：╳(濃化不十分)。
(4)焊料的濕潤性的評價 使用依序實施Ni以及Au鍍覆處理的Cu板，在此Cu板上印刷助焊劑WF-6400(千住金屬工業公司製)，於其上安裝各焊接球。將安裝有焊接球的電極墊，以升溫速度5℃/sec在N2 環境氣體下從25℃升溫至250℃為止，之後1分鐘進行回焊。此類處理在100個焊接球上實施。 (a)100個焊接球全部在電極墊整體上濕潤擴散時：○(良好) (b)1個以上的焊接球在電極墊整體上未濕潤擴散時：╳(不可)。
表1中，顯示合金組成為Sn-7質量%In-3質量%Ag-0.5質量%Cu的各測定結果以及評價結果。且，表1中的In的濃化的評價以未實施熟成處理的焊接球的濃度作為基準。此外，表1中In的單位為質量%。
[表1]
No. 熟成條件 溫度/時間 合金組成 黃色度(b*) 明度(L*) 半定量分析In (質量%) In的濃化 濕潤性
實施例1 常溫/90日期間 Sn-7In-3Ag-0.5Cu 2.83 67.04 7.9 ○ ○
實施例2 200℃/60min Sn-7In-3Ag-0.5Cu 8.33 63.08 10.8 ○ ○
比較例1 0 Sn-7In-3Ag-0.5Cu 2.75 69.11 7.2 ─ ○
比較例2 200℃/120min Sn-7In-3Ag-0.5Cu 15.59 48.00 13.1 ○ ╳
比較例3 200℃/180min Sn-7In-3Ag-0.5Cu 24.40 32.19 14.9 ○ ╳
比較例4 200℃/240min Sn-7In-3Ag-0.5Cu 24.45 33.45 15.4 ○ ╳
比較例5 200℃/300min Sn-7In-3Ag-0.5Cu 22.77 36.90 18.3 ○ ╳
實施例1為對於Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球，在20℃~30℃常溫90日期間，持續暴露在大氣中進行熟成處理。根據實施例1，選定黃色度(b*)為2.83，明度(L*)為67.04的焊接球時，焊接球的表面的In的半定量分析值為7.9質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
實施例2為對於Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球，在200℃60分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例2，選定黃色度(b*)為8.33，明度(L*)為63.08的焊接球時，焊接球的表面的In的半定量分析值為10.8質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。此外，若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，確認能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
比較例1為使用在未進行熟成處理狀態的Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球。比較例1為選定黃色度(b*)為2.75，明度(L*)為69.11的焊接球時，焊接球的表面的In的半定量分析值為7.2質量%。且，在表1中，在比較例1的接合時In是否濃化的評價，由於是以未實施熟成處理的比較例1當作基準，因此不是標記「╳」而是以「─」表示。焊接球的濕潤性的評價為「○」。
比較例2為對於Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球，在200℃120分鐘期間，持續暴露在大氣中進行熟成處理。根據比較例2，選定黃色度(b*)為15.59，明度(L*)為48.00的焊接球時，焊接球的表面的In的半定量分析值為13.1質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。但是，確認由於對應熟成處理的In的濃化使氧化銦變厚，焊料的濕潤性降低。
比較例3為對於Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球，在200℃180分鐘期間，持續暴露在大氣中進行熟成處理。根據比較例3，選定黃色度(b*)為24.40，明度(L*)為32.19的焊接球時，焊接球的表面的In的半定量分析值為14.9質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。但是，確認由於對應熟成處理的In的濃化使氧化銦變厚，焊料的濕潤性降低。
比較例4為對於Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球，在200℃240分鐘期間，持續暴露在大氣中進行熟成處理。根據比較例4，選定黃色度(b*)為24.45，明度(L*)為33.45的焊接球時，焊接球的表面的In的半定量分析值為15.4質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。但是，確認由於對應熟成處理的In的濃化使氧化銦變厚，焊料濕潤性降低。
比較例5為對於Sn-7質量%In-3質量%Ag-0.5質量%Cu的焊接球，在200℃300分鐘期間，持續暴露在大氣中進行熟成處理。根據比較例5，選定黃色度(b*)為22.77，明度(L*)為36.90的焊接球時，焊接球的表面的In的半定量分析值為18.3質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。但是，確認由於對應熟成處理的In的濃化使氧化銦變厚，焊料的濕潤性降低。
表2中，表示合金組成為Sn-1質量%In-0.7質量%Cu的各測定結果以及評價結果。且，表2中的In的濃化的評價是以未實施熟成處理焊接球的濃度作為基準。此外，表2中In的單位為質量%。
[表2]
No. 熟成條件/ 溫度/時間 合金組成 黃色度(b*) 明度(L*) 半定量分析In (質量%) In的濃化 濕潤性
實施例3 常溫/90日期間 Sn-1In-0.7Cu 3.01 67.37 2.1 ○ ○
實施例4 200℃/60min Sn-1In-0.7Cu 4.47 67.33 2.2 ○ ○
實施例5 200℃/120min Sn-1In-0.7Cu 6.20 67.16 2.5 ○ ○
實施例6 200℃/180min Sn-1In-0.7Cu 10.23 65.34 2.7 ○ ○
實施例7 200℃/240min Sn-1In-0.7Cu 12.66 62.15 2.8 ○ ○
比較例6 0 Sn-1In-0.7Cu 2.79 69.30 1.2 ─ ○
比較例7 200℃/300min Sn-1In-0.7Cu 15.30 59.89 3.0 ○ ╳
實施例3為對於Sn-1質量%In-0.7質量%Cu的焊接球，在20℃~30℃的常溫90日期間，持續暴露在大氣中進行熟成處理。根據實施例3，選定黃色度(b*)為3.01，明度(L*)為67.37的焊接球時，焊接球的表面的In的半定量分析值為2.1質量%，確認比起未實施熟成處理比較例6的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
實施例4為對於Sn-1質量%In-0.7質量%Cu的焊接球，在200℃60分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例4，選定黃色度(b*)為4.47，明度(L*)為67.33的焊接球時，焊接球的表面的In的半定量分析值為2.2質量%，確認比起未實施熟成處理比較例6的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
實施例5為對於Sn-1質量%In-0.7質量%Cu的焊接球，在200℃120分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例5，選定黃色度(b*)為6.20，明度(L*)為67.16的焊接球時，焊接球的表面的In的半定量分析值為2.5質量%，確認比起未實施熟成處理比較例6的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
實施例6為對於Sn-1質量%In-0.7質量%Cu的焊接球，在200℃180分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例6，選定黃色度(b*)為10.23，明度(L*)為65.34的焊接球時，焊接球的表面的In的半定量分析值為2.7質量%，確認比起未實施熟成處理比較例6的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
實施例7為對於Sn-1質量%In-0.7質量%Cu的焊接球，在200℃240分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例7，選定黃色度(b*)為12.66，明度(L*)為62.15的焊接球時，焊接球的表面的In的半定量分析值為2.8質量%，確認比起未實施熟成處理比較例6的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
比較例6為使用在未進行熟成處理狀態的Sn-1質量%In-0.7質量%Cu的焊接球。比較例6為選定黃色度(b*)為2.79，明度(L*)為69.30的焊接球時，焊接球的表面的In的半定量分析值為1.2質量%。且，在表2中，比較例6的接合時In是否濃化的評價，由於是以未實施熟成處理的比較例6當作基準，因此不是標記「╳」而是以「─」表示。焊接球的濕潤性的評價為「○」。
比較例7為對於Sn-1質量%In-0.7質量%Cu的焊接球，在200℃300分鐘期間，持續暴露在大氣中進行熟成處理。根據比較例7，選定黃色度(b*)為15.30，明度(L*)為59.89的焊接球時，焊接球的表面的In的半定量分析值為3.0質量%，確認比起未實施熟成處理比較例6的焊接球，In的濃化受到促進。但是，確認由於對應熟成處理的In的濃化使氧化銦變厚，焊料的濕潤性降低。
表3中，表示合金組成為Sn-1質量%In-0.1質量%Bi-0.001質量%Ni-0.7質量%Cu的各測定結果以及評價結果。且，表3中的In的濃化的評價以未實施熟成處理焊接球的濃度當作基準。此外，表3中In的單位為質量%。
[表3]
No. 熟成條件/ 溫度/時間 合金組成 黃色度(b*) 明度(L*) 半定量分析In (質量%) In的濃化 濕潤性
實施例8 200℃/60min Sn-1In-0.1Bi-0.001Ni-0.7Cu 4.61 64.22 2.0 ○ ○
比較例8 0 Sn-1In-0.1Bi-0.001Ni-0.7Cu 2.79 68.76 0.9 ─ ○
實施例8為對於Sn-1質量%In-0.1質量%Bi-0.001質量%Ni-0.7質量%Cu的焊接球，在200℃60分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例8，選定黃色度(b*)為4.61，明度(L*)為64.22的焊接球時，焊接球的表面的In的半定量分析值為2.0質量%，確認比起未實施熟成處理的比較例1的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
比較例8為使用在未進行熟成處理狀態的Sn-1質量%In-0.1質量%Bi-0.001質量%Ni-0.7質量%Cu的焊接球。比較例8為選定黃色度(b*)為2.79，明度(L*)為68.76的焊接球時，焊接球的表面的In的半定量分析值為0.9質量%。且，在表3中，比較例1的接合時In是否濃化的評價，由於是以未實施熟成處理的比較例1當作基準，因此不是標記「╳」而是以「─」表示。焊接球的濕潤性的評價為「○」。
表4中表示合金組成為Sn-1質量%In-0.1質量%Sb-0.001質量%Co-0.7質量%Cu的各測定結果以及評價結果。且，表4中的In的濃化的評價是以未實施熟成處理焊接球的濃度當作基準。此外，在表4中In的單位為質量%。
[表4]
No. 熟成條件/ 溫度/時間 合金組成 黃色度(b*) 明度(L*) 半定量分析In (質量%) In的濃化 濕潤性
實施例9 200℃/60min Sn-1In-0.1Sb-0.001Co-0.7Cu 4.55 63.81 2.5 ○ ○
比較例9 0 Sn-1In-0.1Sb-0.001Co-0.7Cu 2.76 67.21 1.5 ─ ○
實施例9為對於Sn-1質量%In-0.1質量%Sb-0.001質量%Co-0.7質量%Cu的焊接球，在200℃60分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例9，選定黃色度(b*)為4.55，明度(L*)為63.81的焊接球時，焊接球的表面的In的半定量分析值為2.5質量%，確認比起未實施熟成處理比較例9的焊接球，In的濃化受到促進。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
比較例9為使用在未進行熟成處理狀態的Sn-1質量%In-0.1質量%Sb-0.001質量%Co-0.7質量%Cu的焊接球。比較例9為選定黃色度(b*)為2.76，明度(L*)為67.21的焊接球時，焊接球的表面的In的半定量分析值為1.5質量%。且，在表4中，在比較例9的接合時In是否濃化的評價，由於是以未實施熟成處理的比較例9當作基準，因此不是標記「╳」而是以「─」表示。焊接球的濕潤性的評價為「○」。
表5中表示合金組成為Sn-0.1質量%In-0.7質量%Cu的各測定結果以及評價結果。且，表5中的In的濃化的評價是以未實施熟成處理焊接球的濃度當作基準。此外，在表5中In的單位為質量%。
[表5]
No. 熟成條件/溫度/時間 合金組成 黃色度(b*) 明度(L*) 半定量分析In (質量%) In的濃化 濕潤性
實施例10 200℃/60min Sn-0.1In-0.7Cu 4.08 67.35 0.3 ○ ○
比較例10 0 Sn-0.1In-0.7Cu 2.65 70.11 0.1 ─ ○
實施例10為對於Sn-0.1質量%In-0.7質量%Cu的焊接球，在200℃60分鐘期間，持續暴露在大氣中進行熟成處理。根據實施例10，選定黃色度(b*)為4.08，明度(L*)為67.35的焊接球時，焊接球的表面的In的半定量分析值為0.3質量%，確認比起未實施熟成處理比較例10的焊接球，In的濃度增大。此外，確認若在焊接球表面的In的濃化(氧化膜厚)在一定範圍內，能夠良好地維持焊料的濕潤性的同時，亦能夠抑制IMC的成長。
比較例10為使用在未進行熟成處理狀態的Sn-0.1質量%In-0.7質量%Cu的焊接球。比較例10為選定黃色度(b*)為2.65，明度(L*)為70.11的焊接球時，焊接球的表面的In的半定量分析值為0.1質量%。且，在表5中，由於在比較例10的接合時In是否濃化的評價是以未實施熟成處理的比較例10當作基準，因此不是標記「╳」而是以「─」表示。焊接球的濕潤性的評價為「○」。
以上的結果，在In含量為超過0且10質量%以下，球徑為120μm以下的焊接球時，藉由熟成處理可製作黃色度(b*)為2.8以上15.0以下的焊接球，確認在焊接球的表面有In顯著地進行濃化。如此一來，藉由形成在焊接球的表面的含有氧化銦(InO)的氧化膜作為保護膜的作用，相較於未進行熟成處理的一般的焊接球、熟成處理超過一定條件的焊接球，確認在焊接時能夠確保焊料的濕潤性。
且，本發明的技術範圍，不限定於上述實施形態，亦包括在不脫離本發明主旨的範圍中，對上述實施形態添加各種變更者。
無。
無。

Claims (7)

  1. 一種焊接球，In為0.1質量%以上10質量%以上，添加 Ag：0以上4質量%以下， Cu：0以上1.0質量%以下， 選自Bi、Sb的群組合計為0~3質量%， 選自Ni、Co、Fe、Ge、P的群組合計為0~0.1質量% 當中的至少1種以上的元素， 餘份為Sn， 在L*a*b*表色系中的黃色度(b*)為2.8以上15.0以下， 在L*a*b*表色系中的明度(L*)為60以上100以下， (惟，由Ag：3質量%，Cu：0.5質量%，In：0.2質量%，餘份為Sn所構成的焊接球除外)。
  2. 如申請專利範圍第1項所述之焊接球，其中，上述In為0.1質量%以上7質量%以下。
  3. 如申請專利範圍第1項或第2項所述之焊接球，其中，球徑為0.1μm以上120μm以下。
  4. 一種焊接接頭，為使用申請專利範圍第1項或第2項所述之焊接球。
  5. 一種焊接接頭，為使用申請專利範圍第3項所述之焊接球。
  6. 一種接合方法，具有： 將複數個申請專利範圍第1項或第2項所述之焊接球配置在電極上的步驟；以及 將配置在上述電極上的上述複數個焊接球，使用有機酸氣體進行熔融的步驟。
  7. 一種接合方法，具有： 將複數個申請專利範圍第3項所述之焊接球，配置在電極上的步驟；以及 將配置在上述電極上的上述複數個焊接球，使用有機酸氣體進行熔融的步驟。
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