TWI638698B - 金屬球的製造方法、接合材料及金屬球 - Google Patents

金屬球的製造方法、接合材料及金屬球 Download PDF

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TWI638698B
TWI638698B TW104103150A TW104103150A TWI638698B TW I638698 B TWI638698 B TW I638698B TW 104103150 A TW104103150 A TW 104103150A TW 104103150 A TW104103150 A TW 104103150A TW I638698 B TWI638698 B TW I638698B
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metal
ball
metal ball
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TW201544225A (zh
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川浩由
六本木貴弘
相馬大輔
佐藤勇
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千住金屬工業股份有限公司
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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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • 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
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • 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
    • B23K35/302—Cu 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
    • B23K35/24—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
    • B23K35/3033—Ni as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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    • H—ELECTRICITY
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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    • B22F2009/0848—Melting process before atomisation
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    • B22F2301/10—Copper
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    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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
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    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • 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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    • B23K1/008—Soldering within a furnace
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
    • B23K2101/42—Printed circuits
    • 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
    • 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
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Abstract

製造經抑制被放射的α射線量之金屬球。
製造該金屬球係包含以下的步驟：將純金屬在比作為除去對象的不純物之沸點更高、比純金屬的熔點更高且比純金屬的沸點更低的溫度，進行加熱而使純金屬熔融之步驟；及將熔融後的純金屬造球成為球狀之步驟；其中該純金屬，係具有比在純金屬所含有的不純物之中，作為除去對象的不純物之按照氣壓的沸點更高的沸點，U的含量為5ppb以下，Th的含量為5ppb以下，純度為99.9%以上且99.995%以下，而且Pb或Bi的任一者的含量、或Pb及Bi的合計含量為1ppm以上。

Description

金屬球的製造方法、接合材料及金屬球
本發明係有關於一種α射線量為較少的金屬球之製造方法以及使用該製造方法所製成的金屬球、接合材料。
近年來，由於小型資訊機器發達，所搭載的電子零件係進行急速的小型化。為了因應小型化的要求而進行之連接端子的狹小化和封裝面積的縮小化，電子零件係應用在背面設置有電極之設置球格柵陣列(Ball Grid array)(以下，稱為「BGA」)。
應用BGA之電子零件，係例如有半導體組件。在半導體組件，係使用樹脂將具有電極的半導體晶片密封。在半導體晶片的電極係形成有焊料凸塊(solder bump)。該焊料凸塊係藉由將焊料球接合在半導體晶片的電極而成。應用BGA之半導體組件，係以各焊料凸塊與印刷基板的導電性墊(land)接觸的方式被放置在印刷基板上，藉由加熱使熔融的焊料凸塊與墊接合而被搭載在印刷基板上。又，為了因應更高密度封裝的要求，正研討在高度方向堆積半導體組件而成之三維高密度封裝。
但是，在進行三維高密度封裝之半導體組件應用BGA時，半導體組件的自重引起焊料球塌陷掉，致使在電極間 產生連接短路(short)。就進行高密度封裝而言，這種情形係成為故障。
因此，正研討利用Cu(銅)等熔點比焊料更高的金屬所形成的微小直徑金屬球而成之焊料凸塊(例如，參照專利文獻1)。具有金屬球之焊料凸塊，係將電子零件封裝在印刷基板時，即便對焊料凸塊施加半導體組件的重量，藉由在焊料的熔點係不熔融的金屬球而能夠支撐半導體組件。因而，不會有因半導體組件的自重致使焊料凸塊塌陷之情形。
先前技術文獻 專利文獻
[專利文獻1]國際公開第95/24113號公報
雖然電子零件的小型化係使高密度封裝成為可能，但是高密度封裝有引起軟錯誤的問題之情形。軟錯誤係由於α射線進入半導體積體電路(以下，稱為「IC」)的記憶胞(memory cell)中，致使記憶內容有被重寫之可能性。
認為α射線係由於在焊料合金中以不純物的方式含有之鈾(uranium；U)、釷(thorium；Th)、釙(polonium；Po)等的放射性元素產生α崩潰而被放射。因此，係進行開發能夠實現低α射線之組成的焊料合金。
另一方面，在金屬球亦被要求能夠實現低α射線之組成。在此，使用純度高的金屬材料而製造金屬球時，因為含有放射性元素之不純物的含量減少，所以能夠實現低α射 線。但是，成本上升。又，使用純度高的金屬材料來製造金屬球時，雖然金屬球係顯示某種程度接近真球，但是真球度降低。
本發明之課題，係提供一種α射線量較少的金屬球之製造方法及使用該製造方法所製成之真球度高的金屬球、接合材料。
本發明者等得到以下的知識：即便市售之金屬材料的純度為99.9~99.995%，U和Th亦能夠減低至5ppb以下。又，本發明者等係著眼於軟錯誤的原因，係在定量上無法測定程度稍微殘留之210Po等的不純物。而且，本發明者等得到以下的知識：在製造金屬球時的加熱步驟，藉由著眼於不純物的沸點而設定溫度，即便純度為99.995%以下亦能夠將所製成的金屬球之α射線量抑制成為0.0200cph/cm2以下。
又，得到以下的知識：金屬材料的純度為99.995%以下時，能夠抑制真球度的降低。
在此，本發明係如以下。
(1)一種金屬球的製造方法，其特徵在於包含以下的步驟：將純金屬，在按照氣壓而變化的沸點及熔點而設定成為比作為除去對象的不純物之沸點更高、比純金屬的熔點更高且比純金屬的沸點更低的溫度之加熱溫度下，進行加熱而使純金屬熔融之步驟；及將熔融後的純金屬造球成為球狀之步驟；其中該純金屬，係U的含量為5ppb以下，Th的含量為5ppb以下，純度為99.9%以上且99.995%以下，而且Pb或Bi的任一者的含量、或Pb及Bi的合計含量為1ppm以上之純金屬； 相較於在純金屬所含有的不純物之中作為被除去對象的不純物在大氣壓下的沸點，該純金屬在大氣壓下係具有更高的沸點。
(2)如上述(1)所述之金屬球的製造方法，其中純金屬在大氣壓下的熔點為900℃以上且沸點為962℃以上。
(3)如上述(2)所述之金屬球的製造方法，其中除去對象的不純物係Po。
(4)如上述(1)至(3)項中任一項所述之金屬球的製造方法，其中進一步含有將所造球的金屬球進行退火之退火步驟。
(5)一種接合材料，其特徵在於：含有使用如上述(1)至(4)項中任一項所述之製造方法所製成之金屬球。
(6)一種金屬球，使用如上述(1)至(4)項中任一項所述之製造方法所製成，且α射線量為0.0200cph/cm2以下，真球度為0.90以上。
(7)一種接合材料，含有如上述(6)所述之金屬球。
在本發明，能夠製造一種經抑制被放射的α射線量之金屬球。又，能夠提升經抑制被放射的α射線量之金屬球的真球度。
第1圖係顯示鈾崩潰系列之說明圖。
第2圖係顯示釷崩潰系列之說明圖。
第3圖係顯示錒(actinium)崩潰系列之說明圖。
以下，更詳細地說明本發明。在本說明書，有關於金屬球的組成之單位(ppm、ppb、及%)，係只要沒有特別指定，就表示相對於金屬球的質量之比率(質量ppm、質量ppb、及質量%)。
本發明之金屬球的製造方法係包含將純金屬之金屬材料加熱而使其熔融之步驟；及將熔融後的金屬材料進行造球之步驟。在本發明之金屬球的製造方法，係將金屬材料在作為除去對象之不純物的沸點t1以上的加熱溫度下加熱，用以減低在金屬材料所含有的不純物之中，經過經時變化而α崩潰之不純物的含量。
在將金屬材料加熱而使其熔融之步驟，為了在設為不純物的沸點t1以上的加熱溫度T下，使金屬材料熔融且不揮發，將金屬材料的熔點設為t2，將沸點設為t3時，係選擇熔點t2係在不純物的沸點t1附近且沸點t3為不純物的沸點t1以上之金屬材料。加熱溫度T係設定為比金屬材料的沸點t3更低。金屬材料的熔點t2係比焊料更高，使用本發明之製造方法所製成之金屬球，係在焊接時的加熱溫度不熔融。又，因為不純物及金屬材料的沸點及熔點係依照氣壓而變化，所以加熱溫度T係按照氣壓而設定。
在包含此種加熱步驟之金屬球的製造方法，係能夠製造U的含量為5ppb以下，Th的含量為5ppb以下，純度為99.9%以上且99.995%以下，α射線量為0.0200cph/cm2以 下，而且Pb或Bi的任一者的含量、或Pb及Bi的合計含量為1ppm，真球度為0.90以上之金屬球。
作為用以製造此種金屬球之金屬材料，能夠選擇Cu、Ni、Ag、Fe、Co、Au、Nd、Ge等。又，作為金屬材料，Pt、Ti、Lu、Pd、Tm、Sc、Er、Y、Ho、Dy、Tb、Gd、Be、Mn、Pm、Pr、La、Ca、Eu、Yb、Ce、Sr、Ba、Al、Mg、Sb、Te、Cn、Li、In、Ga等。而且，作為金屬材料，能夠選擇W、Re、Os、Ta、Mo、Nb、Ir、Ru、Hf、Tc、Rh、V、Cr、Zr等。
第1圖係顯示鈾崩潰系列之說明圖，第2圖係顯示釷崩潰系列之說明圖，第3圖係顯示錒崩潰系列之說明圖。U、Th等係即便高熔點，但是天然存在比較高的同位素(isotope)本身係成為α射線源，或是經過經時變化引起衰變(decay)而成為α射線源之元素，雖然藉由本發明之製造方法而能夠減低α射線量，但是無法將α射線源降低能夠使用作為軟錯誤對策之水準。因此，在第1圖~第3圖的崩潰系列所顯示之元素，係被從用以製造金屬球之金屬材料除去。
以下，詳述使用本發明之製造方法所製成之金屬球的組成、α射線量、真球度。
．α射線量：0.0200cph/cm2以下
使用本發明之製造方法所製成的金屬球之α射線量係0.0200cph/cm2以下。這是在電子零件的高密度封裝軟錯誤不成為問題的程度之α射線量。在本發明之金屬球的製造方法，係藉由包含在作為除去對象的不純物之210Po能夠揮發的溫度加熱金屬材料之步驟，在金屬材中稍微殘留的210Po係揮發， 相較於金屬材，金屬球係顯示較低的α射線量。從抑制在更高密度封裝產生軟錯誤的觀點而言，α射線量係以0.0020cph/cm2以下為佳，較佳為0.0010cph/cm2以下。
．U：5ppb以下、Th：5ppb以下
U及Th係放射性元素，為了抑制軟錯誤，必須抑制該等的含量。為了使金屬球的α射線量成為0.0200cph/cm2以下，U及Th的含量係各自必須成為5ppb以下。
又，從抑制現在或是將來在高密度封裝產生軟錯誤的觀點而言，U及Th的含量係較佳為各自2ppb以下。
．Pb或Bi的任一者之含量、或Pb及Bi的合計含量為1ppm以上
作為在金屬球所含有的不純物元素，係能夠考慮Sn、Sb、Bi、Ni、Zn、Fe、Al、As、Ag、In、Cd、Cu、Pb；Au、P、S、U、Th等。金屬球係在不純物元素之中，特別是Pb或Bi的任一者之含量、或Pb及Bi的合計含量為1ppm以上作為不純物元素而含有為佳。在本發明，就減低α射線量而言，不必將Pb或Bi的任一者的含量、或Pb及Bi的含量減低至極限為止。這是基於以下的理由。
210Pb係從β崩潰而變化成為210Bi，210Bi係從β崩潰而變化成為210Po，210Po係從α崩潰而變化成為206Pb。因此，為了減低α射線量，認為不純物元素之Pb或Bi的任一者的含量、或Pb及Bi的含量亦以盡力較低為佳。
但是，在Pb所含有的210pb及在Bi所含有的210Bi之含有比係較低。因此，認為只要將Pb和Bi的含量某種程度 減低時，210Pb和210Bi就能夠充分地被除去至能夠將α射線量減低至前述範圍之程度。另一方面，為了提高金屬球的真球度，係如後述，不純物元素的含量係以較高為佳。Pb及Bi的任一者，藉由在金屬材以不純物元素的方式含有，在金屬球的製造步驟之熔融時係成為結晶核，而能夠提高金屬球的真球度。因此，係以能夠將210pb及210Bi除去至能夠將α射線量減低至前述範圍的程度之量，來含有Pb或Bi的任一者、或Pb及Bi為佳。從此種的觀點而言、金屬球係Pb或Bi的任一者的含量、或Pb及Bi的合計含量，以1ppm以上為佳。
Pb或Bi的任一者之含量、或Pb及Bi的合計含量，係較佳為10ppm以上。在能夠得到減低α射線量之範圍，上限值係不被限定，從抑制金屬球的導電度劣化之觀點而言，較佳是Pb或Bi的任一者的含量、或Pb及Bi的合計含量為小於1000ppm。Pb的含量係較佳為10ppm~50ppm，Bi的含量係較佳為10ppm~50ppm。
．金屬球的純度：99.9%以上且99.995%以下
金屬球的純度係3N以上且4N5以下。亦即，金屬球係不純物元素的含量為5ppm以上。在此，Cu等的金屬材料的純度，係將99%設作2N，將99.9%設作3N，將99.99%設作4N。所謂4N5，係表示金屬材料的純度為99.995%。
構成金屬球之金屬材料的純度為該範圍時，在熔融的金屬材料中能夠保用以提高金屬球的真球度之充分量的結晶核。真球度提高之理由係如在以下詳述。
在製造金屬球時，被形成為預定形狀小片之金屬 材料，藉由加熱而熔融且熔融的金屬材料係藉由表面張力而成為球形，其凝固而成為金屬球。在熔融的金屬材料係從液體狀態凝固之過程，結晶粒係在球形之熔融的金屬材料中成長。此時，不純物元素較多時，該不純物元素係成為結晶核而能夠抑制結晶粒的成長。因而，球形的熔融金屬材料，係藉由成長受到抑制之微細結晶粒，而成為真球度高的金屬球。
另一方面，不純物元素為較少時，相對地成為結晶核者較少，粒子成長係未受到抑制且具有某方向性而成長。該結果，球形之熔融的金屬材料之表面的一部分係突出而凝固。此種金屬球係真球度較低。作為不純物元素，能夠考慮Sn、Sb、Bi、Zn、Fe、Al、As、Ag、In、Cd、Cu、Pb、Au、P、S、U、Th等。
純度的下限值係沒有特別限定，就抑制α射線量且抑制因純度降低引起金屬球的導電和熱傳導率劣化之觀點而言，較佳為3N以上。亦即，較佳是除了金屬球的主要金屬材料以外之不純物元素的含量，係小於1000ppm。
．金屬球的真球度：0.90以上
從控制間隙(standoff)高度的觀點而言，金屬球的形狀係以真球度為0.90以上為佳。金屬球的真球度小於0.90時，因為金屬球係成為不定形狀，凸塊形成時係形成高度不均勻的凸塊，致使產生接合不良之可能性提高。真球度係較佳為0.94以上。在本發明，所謂真球度，係表示從真球的偏移。真球度，係例如能夠使用最小二次方中心法(LSC法)、最小區域中心法(MZC法)、最大內接中心法(MIC法)、最小外接中心法(MCC 法)等各種方法來求取。
．金屬球的直徑：1~1000μm
金屬球的直徑係以1~1000μm為佳。在該範圍時，能夠穩定地製造球狀金屬球，又，能夠抑制端子間為狹間距時之連接短路。
<金屬球的製造方法>
本發明之金屬球的製造方法，就在金屬材料所含有的不純物之中產生α崩潰之不純物而言，在本例，為了減低210Po的含量，如果設作比Po的沸點t1更高的溫度且大氣壓下，就是在比Po在大氣壓下沸點t1亦即962℃更高的溫度將金屬材料加熱而使其熔融，來進行造球。藉此，來使金屬材料中的Po揮發且減低從金屬球被放射的α射線量。
(1)Cu球的製造方法
其次，說明Cu球的製造方法作為本發明之金屬球的製造方法的一個例子。當作金屬球之Cu球的材料之Cu材，係被放置在如陶瓷的耐熱性板之耐熱板上，與耐熱板同時在爐中被加熱。在耐熱板之底部，係設置有半球狀之許多圓形溝。溝的直徑和深度，係能夠按照Cu球的粒徑而適當地設定，例如，直徑為0.8mm，深度為0.88mm。又，將Cu細線切斷而得到的晶片形狀Cu材(以下，稱為「晶片材」)，係在耐熱板的溝內各投入一個。
在溝內被投入晶片材之耐熱板，係在經填充有氨分解氣體之爐內，被升溫至比Po在大氣壓下的沸點t1亦即962℃更高的溫度之1100~1300℃，進行加熱處理30~60分鐘。此 時爐內溫度係成為Cu熔點以上時，晶片材係熔融而成為球狀。隨後，爐內係被急冷至室溫(例如25℃)和冷卻氣體溫度為止，Cu球係在耐熱板溝內被成形。冷卻後，成形後的Cu球，係在小於Cu熔點的溫度之800~1000℃再次進行加熱處理。
又，作為另外的方法，係有以下的方法：熔融Cu係從設置在坩堝的底部之孔口滴下，該生成的液滴係被急冷而能夠造球成為Cu球之霧化(atomize)法；及熱電漿將Cu切割金屬加熱至1000℃以上且急冷而造球之方法。如此所造球而成之Cu球，亦可各自在800~1000℃的溫度施行30~60分鐘的再加熱處理。又，在將Cu球造球之前，亦可將Cu球的原料之Cu材於800~1000℃進行加熱處理。
作為Cu球的原料之Cu材，例如能夠使用丸粒狀物、線狀物、柱狀物等。從不使Cu球的純度過度降低之觀點而言，Cu材的純度可為99.9~99.99%。
使用更高純度的Cu材時，亦可不進行上述的加熱處理且亦可將熔融Cu的保持溫度降低至與先前同樣地為1000℃左右。如此，前述的加熱處理亦可按照Cu材的純度和α射線量而適當地省略和變更。又，製成α射線量高的Cu球和異形的Cu球時，亦能夠將該等Cu球再利用作為原料，而且能夠使α射線量降低。
又，亦可將造球後的Cu球退火來進行所謂退火(annealing)之處理。在金屬球的製造，使用純度為3N左右的金屬材料而製造金屬球時，能夠製造真球度高且硬度高的金屬球。另一方面，使用高純度、例如45N5以上的金屬材料而製 造金屬球時，雖然能夠降低硬度，但是係製造真球度較低的金屬球。
因此，為了製造真球度高且降低硬度之金屬球，係在造球後進行退火處理。Cu球時，造球後係例如進行在700℃左右加熱之處理。藉由進行此種退火處理，退火前的維氏硬度為60HV以上者，能夠將硬度降低至小於60HV。
(2)Ni球(鎳球)的製造方法
其次，說明Ni球的製造方法作為本發明之金屬球的製造方法的一個例子。Ni球係能夠使用霧化法來製造。在本發明之所謂霧化法，Ni材係在比Po在大氣壓下的沸點t1亦即962℃更高的溫度之1000℃以上被熔融，液狀熔融Ni係藉由從噴嘴以高速度被噴霧，霧狀熔融Ni被冷卻而造球成為Ni球之方法。就將熔融Ni以高速度從噴嘴噴霧時使用氣體作為介質之情況而言，霧化法係有氣體霧化法等。
又，作為另外的霧化法，亦可以是將熔融Ni從孔口滴下，該生成的液滴係被急冷而造球成為Ni球之方法。在各霧化法所造球而成之Ni球，各自亦可在800~1000℃的溫度施行再加熱處理30~60分鐘。
在該等Ni球的製造方法，亦可在將Ni球造球之前，將Ni球於800~1000℃進行預熱處理。
原料之Ni材，例如能夠使用丸粒狀物、線狀物、板材等。從不使Ni球的純度過度降低之觀點而言，可為2N~4N。
使用此種高純度的Ni材時，亦可不進行上述的加熱處理且亦可將熔融Ni的保持溫度降低至與先前同樣地為 1000℃左右。如此，前述的加熱處理亦可按照Ni材的純度和α射線量而適當地省略和變更。又，製成α射線量高的Ni球和異形的Ni球時，亦能夠將該等Ni球再利用作為原料，而且能夠使α射線量降低。
又，亦可進行將造球後的Ni球退火之退火之處理，用以製造真球度高且降低硬度之Ni球。
<金屬球的應用例>
在本發明之製造方法所製成之Cu球、Ni球等的金屬球，亦能夠應用在焊接材料。為了應用在焊接材料，係在金屬球的表面形成焊料層(鍍焊料被膜)而成為金屬核球即可。
焊料層的組成係合金時，只要以Sn作為主成分之無鉛焊料合金的合金組成，係沒有特別限定。又，作為焊料層，可為鍍Sn被膜。例如可舉出在Sn、Sn-Ag合金、Sn-Cu合金、Sn-Ag-Gu合金、Sn-In合金、及該等添加預定合金元素而成者。任一者均是Sn的含量為40質量%以上。作為添加的合金元素，例如有Ag、Cu、In、Ni、Co、Sb、Ge、P、Fe等。該等之中，從落下衝撃特性的觀點而言，焊料層的合金組成係較佳為Sn-3Ag-0.5Cu合金。
焊料層的厚度係沒有特別限制，較佳是100μm(一側)以下即充分。通常是20~50μm即可。
使用本發明之製造方法所製成之金屬球，係α射線量為0.0200cph/cm2以下，為了使在電子零件的高密度封裝軟錯誤不會成為問題，應用金屬球之金屬核球，亦是將α射線量設為0.0200cph/cm2以下。
因此，在焊料層之U及Th的含量，必須使各自為5ppb以下。又，從抑制現在或將來在高密度封裝產生軟錯誤之觀點而言，U及Th的含量係較佳是各自為2ppb以下。
又，焊料層係頂多在100℃，所以難以認為藉由U、Th、Po等的放射性元素、210Bi及210Pb等的放射性同位素之氣化，使得放射性元素和放射性同位素的含量減低。但是，使鍍覆液和金屬球邊流動邊進行鍍覆時，U、Th、Po、及210Pb、210Bi係在鍍覆液中形成鹽而沈澱。沈澱後的鹽係在電性上為中性，即便鍍覆液流動亦不會混入焊料層中。
因此，焊料層中的放射性元素之含量係顯著地減低。因而，因為應用使用本發明之製造方法所製成的金屬球之金屬核球係被此種焊料層被覆，所以顯示較低的α射線量。從抑制在更高密度封裝產生軟錯誤之觀點而言。α射線量係以0.0020cph/cm2以下為佳，較佳為0.0010cph/cm2以下。
因為形成焊料層之金屬材料的純度越高，亦即不純物的含量越少，放射性元素的含量越減低且α射線源減低，所以不純物量的下限值係沒有特別限定。另一方面，從減低α射線量的觀點而言，上限值係以150ppm以下為佳，較佳為100ppm以下，更佳為50ppm以下，特佳為10ppm以下。
又，焊料層為Sn焊料時，焊料層的純度係焊料層之Sn以外的不純物之合計含量。又，焊料層係Sn-3Ag-0.5Cu的焊料合金時，焊料層的純度係焊料層中的Sn、Ag及Cu以外的不純物之含量的合計。
作為在焊料層所含有的不純物，Sn焊料層時，可舉 出Ag、Ni、Pb、Au、U、Th等。由Sn-Ag-Cu合金所構成之焊料層時，可舉出Sb、Fe、As、In、Ni、Pb、Au、U、Th等。
應用使用本發明之製造方法所製成的金屬球之金屬核球，亦可在形成焊料層之前，預先使用另外的金屬層將金屬球的表面被覆。特別是預先使用Ni層、Co層等將金屬球表面被覆時，相較於金屬球的金屬元素，Ni、Co等的被覆層之金屬元素係較不容易擴散時，能夠減低形成金屬球之金屬材料溶出至焊料層中，而能夠執行作為防擴散層之功能。
構成防擴散層之金屬係不僅是單一金屬，亦可以是由Ni、Co等之中組合2元素以上而成之合金。防擴散層的膜厚係通常為一側0.1~20μm。
又，應用使用本發明之製造方法所製成的金屬球之金屬核球，係在形成焊料層之前，亦可預先進行打底電鍍(strike plating)處理。藉由進行打底電鍍處理，能夠將金屬表面的氧化膜除去，來使金屬球與焊料層的密著性提升。
使用本發明之製造方法所製成的金屬球、應用該金屬球之金屬核球，係能夠使用在電子零件的焊料接頭(solder joint)。又，能夠使用在金屬球或金屬核球係分散在焊料中之泡沫焊料。而且，亦能夠使用在焊料粉末、金屬球或金屬核球、助焊劑混煉而成之焊料膏。在泡沬焊料及焊料膏，係例如能夠使用組成為Sn-3Ag-0.5Cu(各數值為質量%)之焊料合金。又，本發明係不限定於該焊料合金。
又，使用本發明之製造方法所製成的金屬球、應用該金屬球之金屬核球，亦可在表面形成助焊劑層。助焊劑層 係由含有作為活性劑的作用之化合物之1種類或複數種類的成分所構成，其中該活性劑係進行防止金屬表面氧化及除去金屬氧化膜。構成助焊劑層之成分，係以固體狀態附著在金屬球或金屬核球的表面。因此，助焊劑層係在金屬球或金屬核球的表面成為固體而附著，使用在防止金屬球或金屬核球的表面氧化之同時，在焊接時作為將接合對象物的金屬氧化膜除去之活性劑的作用之成分所構成即可。例如，助焊劑層亦可以是由作為活性劑的作用之同時，固定在金屬球或金屬核球之化合物所構成的單一成分所構成。
作為構成助焊劑層之活性劑，係能夠添加胺、有機酸、鹵素的任一者、複數種胺的組合、複數種有機酸的組合、複數種鹵素的組合、單一或複數種胺、有機酸、鹵素的組合。
又，助焊劑層亦可以由作為活性劑的作用之化合物、作為活性輔助劑的作用之化合物等所構成之複數種成分所構成。而且，構成助焊劑層之化合物，例如作為活性劑的作用之化合物，係即便單一時不是固體，只要其他混合物混合而成為固體者即可。
作為構成助焊劑層之活性輔助劑，係按照活性劑的特性而能夠添加酯、醯胺、胺基酸的任一者、複數種酯的組合、複數種醯胺的組合、複數種胺基酸的組合、單一或複數種酯、醯胺、胺基酸的組合。
又，助焊劑層亦可含有松香和樹脂，用以保護作為活性劑的作用之化合物等避免受到回流時的熱之影響。而且，助焊劑層亦可含有使作為活性劑的作用之化合物等固定在 金屬球或金屬核球之樹脂。
助焊劑層係可以由單一或複數種化合物所構成之單一的層。又，助焊劑層亦可以由複數種的化合物所構成之複數層所構成。雖然構成助焊劑層之成分，係以固體狀態附著在金屬球或金屬核球的表面，但是在使助焊劑附著在金屬球或金屬核球之步驟，助焊劑必須成為液狀或氣體狀。
因此，使用溶液塗佈時，構成助焊劑層之成分，必須可溶於溶劑，但是例如形成鹽時，係存在不溶於溶劑中之成分。由於在液狀助焊劑中存在不溶的成分，含有形成沈澱物等難溶解性的成分之助焊劑時，均勻的吸附係變為困難。因此，先前係無法將如形成鹽之化合物混合而構成液狀助焊劑。
相對於此，設作固體狀態而形成每一層助焊劑層且形成多層的助焊劑層時，使用如形成鹽的化合物時，即便是液狀助焊劑時無法混合的成分，亦能夠形成助焊劑層。
使用本發明之製造方法所製成之金屬球、應用該金屬球之金屬核球的使用方法，係除了將焊料膏塗佈在電極上之後，直接將金屬球或金屬核球載置在膏狀物上且接合以外，亦可使用使金屬球或金屬核球分散在焊料中而成之泡沫焊料等。又，亦可與焊料粉末、助焊劑同時混煉及金屬球或金屬核球而作為預先含有金屬球或金屬核球之焊料膏。此時，亦可同時添加不同組成和粒徑之2種類以上的焊料粉末。
而且，亦可將金屬球與聚合物黏結劑、溶劑混煉而作為金屬球膏。作為聚合物黏結劑，能夠使用環氧丙烯酸酯、丙烯醯基樹脂、環氧樹脂、酚樹脂、聚酯樹脂、聚醯亞胺、 聚乙酸乙烯酯等。作為溶劑，能夠使用丁基溶纖劑乙酸酯、苄醇、乙酸乙酯、甲基乙基酮、丁基卡必醇等。
使用上述方法時，與金屬球或金屬核球同時使用之焊料膏和泡沫焊料用焊料合金、焊料膏用焊料粉末的組成係沒有特別限定，針對α射線量，係以0.0200cph/cm2以下為佳。
又，使用本發明之製造方法所製成之Cu球、Ni球等的金屬球，亦能夠應用在導電性接合材料。此時所謂的導電性接合材料，係指為了使用熱硬化性樹脂使其在比導電性金屬粉末(金屬球)的熔點更低的溫度接著而使用者。在本發明，係將焊接材料及導電性接合材料總稱為接合材料。
實施例
以下，說明本發明的金屬球的製造方法之實施例，但是本發明係不被該等限定。
<Cu球的純度與真球度之α射線量的關係>
作為金屬球，係製造純度不同的Cu球而測定真球度及α射線量，來驗證Cu球的純度與真球度之關係及α射線量。
(1)Cu球的製造
實施例1A的Cu球，係使用純度為99.9%(3N)的Cu丸粒而製成。實施例2A的Cu球使用純度為99.995%(4N5)以下的Cu線而製成。比較例1A的Cu球係使用純度大於99.995%(4N5)之Cu板而製成。
將上述的原料使用氣體霧化法而造球。藉此，製成平均粒徑為50μm的Cu球。
(2)Cu球的α射線量之測定方法
α射線量的測定方法係如以下。α射線量的測定係使用氣流比例計數器之α射線測定裝置。測定試樣係在300mm×300mm的平面淺底容器，將Cu球舖滿至無法看到容器的底為止。將該測定試樣放入α射線測定裝置內，在使用PR-10氣流放置24小時之後，測定α射線量。
又，測定時所使用的PR-10氣體(氬90%-甲烷10%)，係將PR-10氣體填充氣體高壓罐之後，經過3星期以上者。使用經過3星期以上的高壓罐，係因為依照在JEDEC(電子工程設計發展聯合協會；Joint Electron Device Engineering Council)所規定之JEDEC STANDARD-Alpha Radiation Measurement in Electronic Materials JESD221(電子材料之JEDEC標準α射線測定JESD221)，使進入氣體高壓罐之大氣中的氡(radon)不引起產生α射線。
(3)Cu球的真球度之測定方法
真球度的測定方法係如以下。真球度係使用CNC影像測定系統測定。在本實施例，係使用Mitutoyo公司製的Ultra Quick Vision、ULTRA QV350-PRO測定裝置，測定Cu球的長徑長度及直徑長度，且算出將500個Cu球各自的直徑除以長徑所得到的值之算術平均值而求取真球度，該值係越接近上限之1.00，係表示越接近真球。
將所製成的Cu球之元素分析結果、真球度及α射線量顯示在表1。在表1之單位，針對U及Th係質量ppb，其他元素係質量ppm。
如表1所顯示、實施例1A的Cu球係純度為3N(99.9%)，實施例2A的Cu球之純度為4N5(99.995%)以下，儘管Bi及Pb的含量為10ppm以上，但是α射線量為小於0.0010cph/cm2且小於被要求之0.0200cph/cm2。因為比較例1A的Cu球係純度高於4N5，當然不用說α射線量為小於0.0010cph/cm2。
又，如表1所顯示、實施例1A及實施例2A的Cu球係純度為4N5以下，因為除了Cu以外之元素的含量為50ppm以上，所以任一者均顯示真球度為0.95以上且滿足0.90以上的條件。另一方面，比較例1A的Cu球係、純度為比4N5更高，因為除了Cu以外之元素的含量為小於50ppm，所以真球度為小於0.90。
<Ni球的純度與真球度與α射線量之關係>
製造純度不同的Ni球作為金屬球而測定真球度及α射線量，來驗證Ni球的純度與真球度的關係及α射線量。
(1)Ni球的製造
實施例1B的Ni球係使用純度為99.9%(3N)的Ni線而製造。在實施例1B所使用的Ni線之α射線量為0.0034cph/cm2，U的含量為0.7ppb，Th的含量為0.5ppb。
實施例2B的Ni球係使用純度為99.995%(4N5)以下的Ni線而製成。在實施例2B所使用的Ni線之純度為99.99%(4N)，α射線量為0.0026cph/cm2，U的含量為小於0.5ppb，Th的含量為小於0.5ppb。
比較例1B的Ni球係使用純度為大於99.995%(4N5) 的Ni板而製成。在比較例1B所使用的Ni板之純度為99.997%(4N7)，α射線量為小於0.0010cph/cm2，U的含量為小於0.5ppb，Th的含量為小於0.5ppb。
將上述的原料投入坩堝之中之後，如果將坩堝的溫度設作在大氣壓下時，就是在比Po在大氣壓下的沸點t1亦即962℃更高的1000℃之溫度條件下進行預熱45分鐘。隨後，將吐出溫度設作1600℃，較佳為1700℃，藉由氣體霧化法而將液狀熔融Ni以高速度從噴嘴噴霧，且將霧狀熔融Ni急冷至室溫而造球成為Ni球。藉此，來製成平均粒徑為50μm的Ni球。
(2)Ni球的α射線量之測定
α射線量的測定方法係與Cu球同樣且使用氣流比例計數器的α射線測定裝置。測定試樣係將Ni球舖滿300mm×300mm的平面淺底容器者。將該測定試樣放入α射線測定裝置內，使用PR-10氣流且放置24小時之後，測定α射線源。
(3)Ni球的真球度的測定
真球度係使用CNC影像測定系統測定。測定方法係與Cu球相同且使用Mitutoyo公司製的Ultra Quick Vision、ULTRA QV350-PRO。
將所製成的Ni球之元素分析結果，α射線量及真球度顯示在表2。在表2之單位，針對U及Th係質量ppb，其他元素係質量ppm。在Ni球，針對U及Th之元素分析係使用高頻感應耦合質量分析(ICP-MS分析)，針對其他元素係使用感應耦合電漿發光分光分析(lCP-AES分析)來進行。
如表2所顯示，儘管實施例1B的Ni球之純度為3N(99.9%)、實施例2B的Ni球之純度為4N5(99.995%)以下，Bi及Pb的含量為10ppm以上，但是α射線量為小於0.0010cph/cm2且小於被要求的0.0200cph/cm2。因為比較例1B的Ni球之純度為比4N5更高，當然不用說α射線量為小於0.0010cph/cm2。又，實施例1B及實施例2B的Ni球，係至少2年期間之α射線量為小於0.0010cph/cm2。因而，因經時變化引起α射線量増加之近年來的問題點，實施例1B及實施例2B的Ni球亦消除了。
又，如表2所顯示，實施例1B及實施例2B的Ni球之純度為4N5以下，因為除了Ni以外之元素的含量為50ppm以上，所以任一者均顯示真球度為0.94以上。另一方面，比較例1B的Ni球之純度比4N5更高，因為除了Ni以外之元素的含量為小於50ppm，所以真球度為小於0.90。
在焊接材料，亦可含有使用本發明之製造方法所製造的金屬球。具體而言，亦可添加在將預發泡焊料、助焊劑及焊料粉末混煉而成之焊料膏等而使用。
又，在本發明之製造方法，亦可追加退火之退火處理步驟，用以減少金屬球的維氏硬度。
從提升生產量和生產速度的觀點而言，所造球而成的金屬球，通常係被急冷至室溫和冷卻氣體溫度。但是，藉由急冷來製造金屬球時，係一剎那地形成金屬元素的結晶粒，在結晶粒成長之前，係由微細的結晶粒形成金屬球。因為由微細的結晶粒所形成的金屬球係較硬且維氏硬度較大，所以對來 自外部的應力之耐久性變低，而有耐落下衝撃性變差之問題。因此，在半導體晶片的封裝所使用的金屬球，係被要求一定的柔軟性，亦即一定值以下的維氏硬度。
因此作為退火處理，係將金屬球在能夠退火的溫度下加熱預定時間，隨後，使用較長的時間將加熱後的金屬球進行緩慢冷卻。藉此，因為金屬球能夠進行再結晶且能夠促進緩慢的結晶成長，所以能夠使金屬元素的結晶粒大大地成長。此時，通常金屬球的真球度係降低。但是，因為在金屬球的最表面所形成的氧化銅係執行作為不純物元素的功能，所以金屬球的最表面之結晶粒係成為微細化的狀態且金屬球不產生非常的真球度降低。又，在退火步驟，α射線量不會増大。
如以上，在本發明之製造方法，藉由施行退火處理步驟，能夠製造α射線量較低、真球度高且耐落下衝撃性良好的金屬球。
具體而言，製造Cu球作為金屬球時，維氏硬度係以20HV以上且60HV以下為佳。維氏硬度大於60HV時，因為對於來自外部的應力之耐久性係變低且耐落下衝撃性變差，同時變為容易產生龜裂。Cu球的維氏硬度小於20HV時，在三維封裝由於半導體晶片等的自重致使Cu球本身產生變形(塌陷)且基板間無法保持適當的空間(間隙高度)。
作為Cu球的退火條件，係將從室溫加熱至700℃之升溫時間設作60分鐘，將在700℃保持之保持時間設為60分鐘，將從700℃冷卻至室溫之冷卻時間設為120分鐘即可。爐內的冷卻係使用在爐內所設置的冷卻風扇來進行。又，亦可 藉由使經施行退火處理之Cu球浸漬在稀硫酸而進行酸處理，用以將因退火處理而在Cu球表面形成的氧化膜除去。

Claims (6)

  1. 一種金屬球的製造方法，其特徵在於包含以下的步驟：將純金屬，在按照氣壓而變化的沸點及熔點而設定成為比作為除去對象的Po之沸點更高、比純金屬的熔點更高且比純金屬的沸點更低的溫度之加熱溫度下，進行加熱而使純金屬熔融之步驟；及將熔融後的純金屬造球成為球狀之步驟；其中該純金屬，係U的含量為5ppb以下，Th的含量為5ppb以下，純度為99.9%以上且99.995%以下，而且Pb的含量為1ppm以上之純金屬；相較於在純金屬所含有的不純物之中作為被除去對象的Po在大氣壓下的沸點，該純金屬在大氣壓下係具有更高的沸點。
  2. 如申請專利範圍第1項所述之金屬球的製造方法，其中純金屬在大氣壓下的熔點為900℃以上且沸點為962℃以上。
  3. 如申請專利範圍第1至2項中任一項所述之金屬球的製造方法，其中進一步含有將所造球的金屬球進行退火之步驟。
  4. 一種接合材料，其特徵在於：含有使用如申請專利範圍第1至3項中任一項所述之製造方法所製成之金屬球。
  5. 一種金屬球，使用如申請專利範圍第1至3項中任一項所述之製造方法所製成，且α射線量為0.0200cph/cm2以下，真球度為0.90以上。
  6. 一種接合材料，含有如申請專利範圍第5項所述之金屬球。
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