TWI754135B - 錫或錫合金的鍍敷液、凸塊的形成方法、電路基板的製造方法 - Google Patents

錫或錫合金的鍍敷液、凸塊的形成方法、電路基板的製造方法 Download PDF

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TWI754135B
TWI754135B TW108109401A TW108109401A TWI754135B TW I754135 B TWI754135 B TW I754135B TW 108109401 A TW108109401 A TW 108109401A TW 108109401 A TW108109401 A TW 108109401A TW I754135 B TWI754135 B TW I754135B
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Prior art keywords
tin
acid
plating solution
tin alloy
plating
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TW108109401A
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TW201940747A (zh
Inventor
渡邉眞美
薄京佳
中矢清
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日商三菱綜合材料股份有限公司
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Priority claimed from JP2018052012A external-priority patent/JP6635139B2/ja
Priority claimed from JP2019040216A external-priority patent/JP6677873B2/ja
Application filed by 日商三菱綜合材料股份有限公司 filed Critical 日商三菱綜合材料股份有限公司
Publication of TW201940747A publication Critical patent/TW201940747A/zh
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
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    • C25D7/00—Electroplating characterised by the article coated
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Abstract

此錫或錫合金的鍍敷液係包含：(A)至少包含亞錫鹽之可溶性鹽；(B)選自有機酸及無機酸的酸或其鹽；(C)界面活性劑；(D)調平劑；及(E)添加劑，前述界面活性劑係以下通式(1)所示之化合物(C1)及/或通式(2)所示之化合物(C2)：

Description

錫或錫合金的鍍敷液、凸塊的形成方法、電路基板的製造方法
本發明係有關於一種在將半導體積體電路晶片搭載於電路基板時，用以在基板上製造作為錫或錫合金之突起電極的凸塊之錫或錫合金的鍍敷液、使用其之凸塊的形成方法及電路基板的製造方法。更詳而言之，係有關於一種縱為凸塊徑或凸塊間距不同的圖型，對基板上之通孔的通孔填充性亦優良，而且形成之凸塊的高度呈均等之錫或錫合金的鍍敷液。 本案係基於2018年3月20日於日本所申請之日本特願2018-52012號、2018年3月26日於日本所申請之日本特願2018-57551號及2019年3月6日於日本所申請之日本特願2019-40216號，主張其優先權，將其內容援用於此。
搭載半導體積體電路晶片(以下稱半導體晶片)之電路基板，為了因應輕薄小型(輕量化、薄型化、小型化)，目前主要在於製造CSP(Chip Size/scale Package)型半導體裝置，其係將封裝體基板面積縮小成與搭載於基板之半導體晶片幾乎相等的程度。為了連接此電路基板與半導體晶片，而將基板側之通孔主體部的通孔開口部以錫或錫合金填充而形成突起狀之金屬端子的突起電極，亦即形成凸塊，並對此凸塊裝填半導體晶片。
以往，要藉由此錫或錫合金材料之填充來形成凸塊，而需將錫系焊膏等導電性膏或錫系焊球填充於通孔主體部，或者使用錫或錫合金的鍍敷液以電鍍法於通孔內形成鍍錫堆積層，接著藉由熱處理使導電性膏、焊球或鍍錫堆積層熔融。
茲參照圖1說明以電鍍法形成凸塊的一般方法。如圖1(a)所示，係在施有配線等的基板1的表面，藉由使用阻焊劑的微影法形成具有開口部的阻焊劑圖型。其次，在阻焊劑層2的表面藉由無電解電鍍形成供電用之銅種子層3。其次，在銅種子層3的表面形成乾膜阻劑層4，並以與阻焊劑層2之開口部連接的方式形成具有開口部的乾膜阻劑圖型。接著，透過上述銅種子層3進行供電，於乾膜阻劑圖型之通孔6的內部進行錫電鍍，而於銅種子層3上的通孔6內形成鍍錫堆積層7(鍍錫皮膜)。其次，依序去除乾膜阻劑層4與銅種子層3，接著藉由回焊處理將殘留的鍍錫堆積層7熔融，而如圖1(b)所示形成錫凸塊8。
迄此，已有人完成在使用電鍍法形成錫或錫合金凸塊時，藉由改變錫或錫合金的鍍敷液之含有成分，而改良對基板上之通孔的通孔填充性或抑制凸塊內的空隙之相關的改善作業(例如參照專利文獻1、2、3、4)。
專利文獻1中揭示一種錫或錫合金的鍍敷液，其係包含特定的α,β-不飽和醛或特定的α,β-不飽和酮的化合物。此專利文獻1中載有以下事項。 此鍍敷液其通孔填充性高，若使用此鍍敷液，則錫鍍層會選擇性地堆積於凹部內，而能夠獲得實質上不具有空隙的鍍錫堆積物。 由於形成之鍍錫皮膜表面未發生色斑或異常析出，故可獲得焊接性或耐變色性等優良、實用且具有良好外觀的鍍錫皮膜。 就此鍍敷液，由於通孔填充性高，而能夠形成實質上不具有空隙的柱狀鍍錫堆積物(凸塊)。
又，專利文獻2中揭示一種錫或錫合金的鍍敷液，其係含有(a)含羧基化合物與(b)含羰基化合物，成分(a)為1.3g/L以上及成分(b)為0.3g/L以上。此專利文獻2中載有以下事項。 透過使用此鍍敷液，對具有盲孔或貫通孔的被鍍物進行電鍍，可於短時間內以高可靠性填充盲孔或貫通孔。 可利用於半導體的三維安裝、印刷配線板之盲孔或貫通孔的填充步驟或矽貫通電極的形成。
此外，專利文獻3中揭示一種錫或錫合金的鍍敷液，其係包含無機酸及有機酸以及其水溶性鹽、界面活性劑與調平劑。於此，界面活性劑係選自由聚氧化烯苯基醚或其鹽，及聚氧化烯多環苯基醚或其鹽所成群組的至少一種非離子界面活性劑。構成聚氧化烯苯基醚之苯基，及構成聚氧化烯多環苯基醚之多環苯基亦可經碳數1～24之烷基或羥基取代。調平劑係選自由脂肪族醛、芳香族醛、脂肪族酮及芳香族酮所成群組的至少一種；及α,β-不飽和羧酸或者其醯胺、或該等之鹽。此專利文獻3中載有以下事項。 由於包含特定的非離子界面活性劑與特定的二種調平劑，凹坑掩埋性優良，而且可抑制空隙的產生。藉此，若使用此鍍敷液，則可提供一種無凹坑、呈平滑，且回焊後亦未產生空隙的良好之凸塊。
再者，專利文獻4中揭示一種突起電極形成用之錫或錫合金的電鍍液，其含有：(A)由亞錫鹽，與亞錫鹽及選自銀、銅、鉍、鎳、銦、金之金屬的鹽之混合物的任一種所構成的可溶性鹽；(B)酸或其鹽；(C)選自由芳香族及脂肪族醛、芳香族及脂肪族酮、不飽和羧酸類、芳香族羧酸類所成群組的填充用有機化合物；及(D)非離子系界面活性劑。此專利文獻4中載有以下事項。 此鍍敷液由於除抑制錫系材料的析出之特定的化合物(C)外亦組合使用成分(D)，可有效抑制通孔上部的析出，能使錫系材料的析出從通孔底部優先地朝通孔上方進行。因此，可防止空隙的產生並可順利地填滿通孔。由此，可進行回焊而良好地形成突起電極，或者無須進行回焊即可良好地形成突起電極，接合強度或電特性優異。
近年來，係逐漸演變成在一電路基板上混合存在凸塊徑或凸塊間距不同的配線圖型。就此種複雜的配線圖型，當凸塊徑或凸塊間距不同時仍要求所有的凸塊係以均等的高度形成。根據上述專利文獻1～4之錫或錫合金的鍍敷液，有可抑制凸塊內之空隙的產生，可於短時間內以高可靠性填充基板上的通孔，且通孔填充性或外觀優良之特長。然而，該等專利文獻1～4中的基板用鍍敷液，並未以謀求凸塊的高度均等性為其課題。
具體而言，如圖2所示，若為凸塊徑不同的圖型時，若使用習知錫或錫合金的鍍敷液來進行鍍敷，雖可改良小徑或大徑之任一者的通孔填充性，但另一者的通孔填充性會變差。亦即，在存有兩種小徑及大徑之通孔6的基板上，對兩種通孔6同時進行鍍敷時，不易以良好的通孔填充性對兩種通孔6進行鍍敷。如此，存在通孔填充性相異的通孔6時(圖2(b))，回焊後之凸塊8的高度不均度較大，而無法達到凸塊8的高度均等性(圖2(d))。從而，要達到凸塊8的高度均等性(圖2(c))，則需如圖2(a)所示，改善對小徑及大徑之兩種通孔6的通孔填充性。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2014-125662號公報(請求項2、段落[0020]) [專利文獻2]日本特開2015-007276號公報(請求項1、段落[0011]、[0012]) [專利文獻3]日本特開2015-193916號公報(請求項1、段落[0019]) [專利文獻4]日本特開2016-074963號公報(請求項1、段落[0019])
[發明所欲解決之課題]
本發明目的在於提供一種縱為凸塊徑不同的圖型，對基板上之通孔的通孔填充性亦優良，而且形成之凸塊的高度呈均等之錫或錫合金的鍍敷液。 [解決課題之手段]
本發明第1態樣係一種錫或錫合金的鍍敷液，其係包含：(A)至少包含亞錫鹽之可溶性鹽；(B)選自有機酸及無機酸的酸或其鹽；(C)界面活性劑；(D)調平劑；及(E)添加劑，前述界面活性劑係以下通式(1)所示之化合物(C1)及/或通式(2)所示之化合物(C2)。 式(1)中，R為碳數7～13之烷基，m為5～11，n為0～3，m與n相異。又，式(2)中，R為碳數7～13之烷基，m為5～11，n為1～3，m與n相異。
Figure 02_image007
Figure 02_image009
本發明第2態樣係第1態樣之錫或錫合金的鍍敷液，其中前述添加劑係包含選自有別於前述2種界面活性劑(C1,C2)之界面活性劑、抗氧化劑及碳數1～3之醇的2種以上。
本發明第3態樣係一種凸塊的形成方法，其係具有：使用如第1或第2態樣之錫或錫合金的鍍敷液，於基板上形成錫或錫合金的鍍敷堆積層之步驟；及其次，進行回焊處理而形成凸塊之步驟。
本發明第4態樣係一種電路基板的製造方法，其係使用藉由如第3態樣之方法所形成的凸塊來製造電路基板。 [發明之效果]
就本發明第1態樣之錫或錫合金的鍍敷液，透過界面活性劑(C1,C2)具有使通式(1)及通式(2)中的聚氧丙烯烷基數m及聚氧乙烯基數n各自處於既定範圍之特定的非離子(nonionic)結構，於鍍敷時，可抑制Sn離子的析出，而對鍍敷對象表面良好地進行鍍敷。尤其是根據此鍍敷液，若為凸塊徑不同的圖型時，即使凸塊徑較大或較小，對基板上之通孔的通孔填充性亦優良，而且形成之凸塊的高度呈均等。研判此係極化電阻增大所致。
就本發明第2態樣之錫或錫合金的鍍敷液，藉由進一步包含選自有別於2種界面活性劑(C1,C2)之界面活性劑、抗氧化劑及碳數1～3之醇的2種以上，可發揮以下效果。有別於2種界面活性劑(C1,C2)之界面活性劑可發揮穩定鍍敷液、提升溶解性等效果。又，抗氧化劑可防止可溶性亞錫鹽氧化成為正錫鹽。再者，醇可發揮提升界面活性劑的溶解性之效果。
就本發明第3態樣之方法，係使用第1或第2態樣之錫或錫合金的鍍敷液，於基板上形成錫或錫合金的鍍敷堆積層，其次進行回焊處理而形成凸塊。藉此，縱為凸塊徑不同的圖型，仍可形成高度均等的凸塊。
就本發明第4態樣之方法，係使用藉由第3態樣之方法所形成的凸塊來製造電路基板。藉此，可製作無電性連接不良的高可靠性半導體裝置。
[實施發明之形態]
以下說明實施本發明之形態。
本實施形態之錫或錫合金的鍍敷液係包含：(A)至少包含亞錫鹽之可溶性鹽；(B)選自有機酸及無機酸的酸或其鹽；(C)界面活性劑；(D)調平劑；及(E)添加劑。其餘部分為屬溶劑的水。此界面活性劑係上述通式(1)所示之化合物(C1)及/或上述通式(2)所示之化合物(C2)。
上述可溶性鹽係由亞錫鹽，與此亞錫鹽及選自由銀、銅、鉍、鎳、銻、銦、鋅所成群組之金屬的鹽的混合物之任一者所構成。
本實施形態之錫合金係錫與選自銀、銅、鉍、鎳、銻、銦、鋅之既定金屬的合金，可舉出例如錫-銀合金、錫-銅合金、錫-鉍合金、錫-鎳合金、錫-銻合金、錫-銦合金、錫-鋅合金的二元合金、錫-銅-鉍、錫-銅-銀合金等的三元合金。
從而，本實施形態之可溶性鹽(A)係指可於鍍敷液中生成Sn2+ 、Ag+ 、Cu+ 、Cu2+ 、Bi3+ 、Ni2+ 、Sb3+ 、In3+ 、Zn2+ 等各種金屬離子的任意可溶性鹽，可舉出例如該金屬的氧化物、鹵化物、無機酸或有機酸的該金屬鹽等。
作為金屬氧化物，可舉例氧化亞錫、氧化銅、氧化鎳、氧化鉍、氧化銻、氧化銦、氧化鋅等；作為金屬的鹵化物，可舉例氯化亞錫、氯化鉍、溴化鉍、氯化亞銅、氯化銅、氯化鎳、氯化銻、氯化銦、氯化鋅等。
作為無機酸或有機酸的金屬鹽，可舉例硫酸銅、硫酸亞錫、硫酸鉍、硫酸鎳、硫酸銻、硝酸鉍、硝酸銀、硝酸銅、硝酸銻、硝酸銦、硝酸鎳、硝酸鋅、乙酸銅、乙酸鎳、碳酸鎳、錫酸鈉、氟硼酸亞錫、甲烷磺酸亞錫、甲烷磺酸銀、甲烷磺酸銅、甲烷磺酸鉍、甲烷磺酸鎳、甲烷磺酸銦、二甲烷磺酸鋅、乙烷磺酸亞錫、2-羥基丙烷磺酸鉍等。
本實施形態之酸或其鹽(B)係選自有機酸及無機酸或其鹽。上述有機酸可舉出烷磺酸、烷醇磺酸、芳香族磺酸等的有機磺酸、或脂肪族羧酸等。無機酸可舉出氟硼酸、氫矽氟酸、胺基磺酸、鹽酸、硫酸、硝酸、過氯酸等。其鹽為鹼金屬的鹽、鹼土金屬的鹽、銨鹽、胺鹽、磺酸鹽等。基於金屬鹽的溶解性或排水處理的容易性觀點，該成分(B)較佳為有機磺酸。
作為上述烷磺酸，可使用化學式Cn H2n+1 SO3 H(例如n=1~5，較佳為1~3)所示者，具體而言可舉例甲烷磺酸、乙烷磺酸、1-丙烷磺酸、2-丙烷磺酸、1-丁烷磺酸、2-丁烷磺酸、戊烷磺酸等，或己烷磺酸、癸烷磺酸、十二烷磺酸等。
作為上述烷醇磺酸，可使用化學式 Cp H2p+1 -CH(OH)-Cq H2q -SO3 H(例如p=0~6、q=1~5)所示者，具體而言可舉例2-羥基乙烷-1-磺酸、2-羥基丙烷-1-磺酸、2-羥基丁烷-1-磺酸、2-羥基戊烷-1-磺酸等，或1-羥基丙烷-2-磺酸、3-羥基丙烷-1-磺酸、4-羥基丁烷-1-磺酸、2-羥基己烷-1-磺酸、2-羥基癸烷-1-磺酸、2-羥基十二烷-1-磺酸等。
上述芳香族磺酸，基本上為苯磺酸、烷基苯磺酸、苯酚磺酸、萘磺酸、烷基萘磺酸等，具體可舉出1-萘磺酸、2-萘磺酸、甲苯磺酸、二甲苯磺酸、p-苯酚磺酸、甲酚磺酸、磺基水楊酸、硝基苯磺酸、磺基苯甲酸、二苯基胺-4-磺酸等。
作為上述脂肪族羧酸，可舉例如乙酸、丙酸、丁酸、檸檬酸、酒石酸、葡糖酸、磺基琥珀酸、三氟乙酸等。
本實施形態之界面活性劑(C)所含之非離子系界面活性劑(C1)係以下通式(1)所示之聚氧乙烯與聚氧丙烯烷基醚的縮合物、或聚氧乙烯烷基醚。
Figure 02_image011
式(1)中，R為碳數7～13之烷基，m為5～11，n為0～3，m與n相異。此外，R之烷基可為直鏈，亦可具有支鏈。R的碳數若未達7，會有發生鍍敷之外觀異常的不良狀況。R的碳數若超過13，則會有不易溶解於鍍敷液中、通孔填充性差或發生鍍敷之外觀異常的不良狀況。此外，R的碳數較佳為10～12。又，m若未達5，會有不易溶解於鍍敷液中或發生鍍敷之外觀異常的不良狀況。m若超過11，則會有通孔填充性差的不良狀況。此外，m較佳為6～10。再者，n若超過3，會有不易溶解於鍍敷液中或發生鍍敷之外觀異常的不良狀況。此外，n較佳為0～2。
本實施形態之界面活性劑(C)所含之非離子系界面活性劑(C2)係以下通式(2)所示之聚氧丙烯與聚氧乙烯烷基醚的縮合物。
Figure 02_image013
式(2)中，R為碳數7～13之烷基，m為5～11，n為1～3，m與n相異。此外，R之烷基可為直鏈，亦可具有支鏈。R的碳數若未達7，會有發生鍍敷之外觀異常的不良狀況。R的碳數若超過13，則會有不易溶解於鍍敷液中、通孔填充性差或發生鍍敷之外觀異常的不良狀況。此外，R的碳數較佳為10～12。又，m若未達5，會有不易溶解於鍍敷液中或發生鍍敷之外觀異常的不良狀況。m若超過11，則會有通孔填充性差的不良狀況。此外，m較佳為6～10。再者，n若超過3，會有不易溶解於鍍敷液中或發生鍍敷之外觀異常的不良狀況。此外，n較佳為1～2。
本實施形態之調平劑(D)係為了均勻且緻密地形成鍍敷皮膜並使鍍敷皮膜呈平滑而含有。而且，為了提高通孔填充性而抑制空隙的產生，係使用第1調平劑(D-1)及第2調平劑(D-2)此2種。作為第1調平劑(D-1)，可舉出選自由脂肪族醛、芳香族醛、脂肪族酮及芳香族酮所成群組的1種或2種以上；作為第2調平劑(D-2)，可舉出α,β-不飽和羧酸或其醯胺、或該等之鹽。
第1調平劑(D-1)係包含醛或酮的羰基化合物，不包含第2調平劑(D-2)的α,β-不飽和羧酸。具體而言可例示以下者。作為脂肪族醛，可舉出甲醛、乙醛、烯丙醛等。又，作為芳香族醛，可舉出苯甲醛、2-氯苯甲醛、3-氯苯甲醛、4-氯苯甲醛、2,4-二氯苯甲醛、2,6-二氯苯甲醛、2,4,6-三氯苯甲醛、1-萘甲醛、2-萘甲醛、2-羥基苯甲醛、3-羥基苯甲醛、4-羥基苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、間大茴香醛、鄰大茴香醛、對大茴香醛等。又，作為脂肪族酮，可舉出乙醯基丙酮等。再者，作為芳香族酮，可舉出亞苄基丙酮(與苄叉丙酮同義)、2-氯苯乙酮、3-氯苯乙酮、4-氯苯乙酮、2,4-二氯苯乙酮、2,4,6-三氯苯乙酮等。此等可單獨使用，亦可使用2種以上。第1調平劑(D-1)在電鍍浴中所佔之較佳含量(單獨含有時為其單獨的量，含有2種以上實則為該等的合計量)為0.001g/L～0.3g/L，更佳為0.01g/L～0.25g/L。上述成分的含量偏少時，其添加效果不足；另外，上述成分的含量過多時，則有妨害鍍敷皮膜的平滑化之虞。
作為第2調平劑(D-2)，可舉出丙烯酸、甲基丙烯酸、2-吡啶甲酸、巴豆酸、3-氯丙烯酸、3,3-二甲基丙烯酸、2,3-二甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸2-乙基己酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基丙酯、甲基丙烯酸2-二甲基胺基乙酯、甲基丙烯酸酐、甲基丙烯酸甲酯等。又，第2調平劑(D-2)亦包含α,β-不飽和羧酸之醯胺(例如丙烯醯胺等)、或α,β-不飽和羧酸之鹽(例如鉀、鈉、銨等之鹽)。第2調平劑(D-2)在電鍍浴中所佔之較佳含量(單獨含有時為其單獨的量，含有2種以上實則為該等的合計量)為0.01g/L～50g/L，更佳為0.05g/L～10g/L。上述成分的含量偏少時，其添加效果不足；另外，上述成分的含量過多時，則有妨害鍍敷皮膜的平滑化之虞。
本實施形態之添加劑(E)係添加於錫或錫合金的鍍敷液的各種添加劑。添加劑(E)較佳包含選自有別於前述2種界面活性劑(C1,C2)之界面活性劑、抗氧化劑及碳數1～3之醇的2種以上。
作為此時的其他界面活性劑，可舉出一般的陰離子系界面活性劑、陽離子系界面活性劑、非離子系界面活性劑及兩性界面活性劑。
作為陰離子系界面活性劑，可舉例聚氧乙烯(1莫耳分子中含有環氧乙烷：12莫耳)壬基醚硫酸鈉等的聚氧化烯烷基醚硫酸鹽；聚氧乙烯(1莫耳分子中含有環氧乙烷：12莫耳)十二烷基苯基醚硫酸鈉等的聚氧化烯烷基苯基醚硫酸鹽；十二烷基苯磺酸鈉等的烷基苯磺酸鹽；1-萘酚-4-磺酸鈉、2-萘酚-3,6-二磺酸二鈉等的萘酚磺酸鹽；二異丙基萘磺酸鈉、二丁基萘磺酸鈉等的(聚)烷基萘磺酸鹽；十二烷基硫酸鈉、油烯基硫酸鈉等的烷基硫酸鹽等。
作為陽離子系界面活性劑，可舉例單烷基胺鹽、二烷基胺鹽、三烷基胺鹽、二甲基二烷基銨鹽、三甲基烷基銨鹽、十二烷基三甲基銨鹽、十六烷基三甲基銨鹽、十八烷基三甲基銨鹽、十二烷基二甲基銨鹽、十八烯基二甲基乙基銨鹽、十二烷基二甲基苄基銨鹽、十六烷基二甲基苄基銨鹽、十八烷基二甲基苄基銨鹽、三甲基苄基銨鹽、三乙基苄基銨鹽、十六烷基吡啶鎓鹽、十二烷基吡啶鎓鹽、十二烷基甲基吡啶鎓鹽、十二烷基咪唑啉鎓鹽、油烯基咪唑啉鎓鹽、十八烷基胺乙酸鹽、十二烷基胺乙酸鹽等。
作為非離子系界面活性劑，可舉例糖酯、脂肪酸酯、C1 ~C25 烷氧基磷酸(鹽)、去水山梨醇酯、矽系聚氧乙烯醚、矽系聚氧乙烯酯、氟系聚氧乙烯醚、氟系聚氧乙烯酯、環氧乙烷及/或環氧丙烷與烷基胺或二胺的縮合生成物的硫酸化或者磺化加成物、聚氧乙烯異丙苯基苯基醚(惟EO鏈為10～14)等。
作為兩性界面活性劑，可舉例甜菜鹼、羧基甜菜鹼、咪唑啉鎓甜菜鹼、磺基甜菜鹼、胺基羧酸等。
上述抗氧化劑係使用於防止可溶性亞錫鹽氧化成為正錫鹽。 作為抗氧化劑，可舉例次磷酸類、抗壞血酸或其鹽、苯酚磺酸(Na)、甲酚磺酸(Na)、對苯二酚磺酸(Na)、對苯二酚、α或β-萘酚、鄰苯二酚、間苯二酚、間苯三酚、肼、苯酚磺酸、鄰苯二酚磺酸、羥基苯磺酸、萘酚磺酸、或該等的鹽等。
上述碳數為1～3之醇係使用於提升上述界面活性劑的溶解性。作為醇，可舉例甲醇、乙醇、1-丙醇、2-丙醇等。醇可單獨使用1種或組合使用2種以上。
單獨使用本實施形態之非離子系界面活性劑(C1或C2)時，非離子系界面活性劑(C1或C2)在鍍敷液中的含量為0.5g/L～50g/L，較佳為1g/L～5g/L。含量若未達下限值，會因供給過多的Sn離子而產生枝晶等鍍敷問題。又，含量若超過上限值，則有Sn離子不易到達鍍敷對象表面，而通孔填充性較差的不良狀況。使用非離子系界面活性劑(C1)與非離子系界面活性劑(C2)此兩者時，宜使非離子系界面活性劑(C1)的含量與非離子系界面活性劑(C2)的含量之合計量成上述範圍內。
又，作為可溶性金屬鹽(A)，可僅使用上述化合物的1種或使用2種以上，其在鍍敷液中的含量為30g/L～100g/L，較佳為40g/L～60g/L。含量少於適當範圍時，生產性會變差；含量較多的話，則鍍敷液成本會提高。
作為無機酸、有機酸或其鹽(B)，可僅使用上述化合物的1種或使用2種以上，其在鍍敷液中的含量為80～300g/L，較佳為100～200g/L。含量少於適當範圍時，導電率較低而導致電壓上升。含量較多的話，則鍍敷液的黏度會上升而使得鍍敷液的攪拌速度降低。 添加劑(E)在鍍敷液中的含量為0.5g/L～50g/L，較佳為1g/L～5g/L。
另一方面，本實施形態之電鍍液的液溫一般為70℃以下，較佳為10℃～40℃。藉由電鍍形成鍍敷膜時的電流密度為0.1A/dm2 以上100A/dm2 以下的範圍，較佳為0.5A/dm2 以上20A/dm2 以下的範圍。電流密度過低的話，生產性會變差；過高的話，則凸塊的高度均等性會變差。
若將本實施形態之單獨包含非離子系界面活性劑(C1及/或C2)、或者包含非離子系界面活性劑(C1)與非離子系界面活性劑(C2)此兩者作為界面活性劑之錫或錫合金的鍍敷液應用於被鍍物之電路基板，並將液溫與電流密度設定為上述範圍，則可於此電路基板上形成既定的金屬皮膜(錫或錫合金的鍍敷堆積層)。接著進行回焊處理，便可形成凸塊。 若將半導體晶片裝填於如此形成之凸塊上，則可製造搭載有半導體晶片的電路基板。 作為電路基板，可舉出印刷電路基板、可撓式印刷電路基板、半導體積體電路基板等。 [實施例]
其次，對本發明之實施例連同比較例詳細加以說明。
(實施例及比較例中所使用之非離子系界面活性劑(C1)) 將作為實施例1～8、13、14及比較例1～10中所使用之非離子系界面活性劑(C1)的聚氧乙烯與聚氧丙烯烷基醚的縮合物或聚氧乙烯烷基醚(C1-1～C1-17)之各結構式(1)中的R的碳數、聚氧乙烯(EO)基的m數、聚氧丙烯(PO)基的n數分別示於表1。
(實施例及比較例中所使用之非離子系界面活性劑(C2)) 將實施例1、2、9～14及比較例11～16中所使用之非離子系界面活性劑(C2)的聚氧丙烯與聚氧乙烯烷基醚的縮合物(C2-1～C2-10)之各結構式(1)中的R的碳數、聚氧乙烯(EO)基的m數、聚氧丙烯(PO)基的n數分別示於表2。此外，R的碳數、m、n之值數係藉由1 H-NMR求得。
Figure 02_image015
Figure 02_image017
(Sn鍍敷液的準備) ＜實施例1＞ 在甲烷磺酸錫水溶液中混合作為游離酸之甲烷磺酸、作為抗氧化劑之對苯二酚、作為調平劑(D-1)之1-萘甲醛及作為調平劑(D-2)之甲基丙烯酸，而調成均勻的溶液。其次，進一步添加作為界面活性劑之上述No.C1-6之聚氧乙烯烷基醚(質量平均分子量：500、式(1)中之R的碳數：13、聚氧乙烯(EO)基的m數：6、聚氧丙烯(PO)基的n數：0)及上述No.C2-2之聚氧乙烯與聚氧丙烯烷基醚的縮合物(質量平均分子量：530、式(2)中之R的碳數：9、聚氧乙烯(EO)基的m數：6、聚氧丙烯(PO)基的n數：2)。然後，最終添加離子交換水，而準備下述組成之Sn鍍敷液。此外，甲烷磺酸錫水溶液係藉由對金屬Sn板在甲烷磺酸水溶液中進行電解而調製。
(Sn鍍敷液的組成) 甲烷磺酸Sn(作為Sn2+ )：50g/L 甲烷磺酸鉀(作為游離酸)：100g/L 非離子系界面活性劑C1-6：2g/L 非離子系界面活性劑C2-2：2g/L 對苯二酚(作為抗氧化劑)：1g/L 1-萘甲醛(作為調平劑(D-1))：0.1g/L 甲基丙烯酸(作為調平劑(D-2))：2g/L 離子交換水：其餘部分
＜實施例3～5、7～9、11、12、14及比較例1、2、4、5、7、9、10、12、13、15、16＞ 就實施例3～5、7～9、11、12、14及比較例1、2、4、5、7、9、10、12、13、15、16，作為非離子系界面活性劑(C1)及非離子系界面活性劑(C2)，係使用表1及表2所示性質之界面活性劑，而如表3及表4所示地選定。除此之外係以實施例1同樣的方式，準備實施例3～5、7～9、11、12、14及比較例1、2、4、5、7、9、10、12、13、15、16之Sn鍍敷液。
(SnAg鍍敷液的準備) ＜實施例2＞ 在甲烷磺酸錫水溶液中混合作為游離酸之甲烷磺酸、作為抗氧化劑之鄰苯二酚、作為調平劑(D-1)之苯甲醛及作為調平劑(D-2)之甲基丙烯酸甲酯而使其溶解。進一步添加甲烷磺酸銀液並加以混合。藉由混合而調成均勻的溶液。其次，進一步添加作為界面活性劑之上述No.C1-6之聚氧乙烯與聚氧丙烯烷基醚的縮合物(質量平均分子量：500、式(1)中之R的碳數：13、聚氧乙烯(EO)基的m數：6、聚氧丙烯(PO)基的n數：0)及上述No.C2-3之聚氧乙烯與聚氧丙烯烷基醚的縮合物(質量平均分子量：650、式(2)中之R的碳數：13、聚氧乙烯(EO)基的m數：8、聚氧丙烯(PO)基的n數：2)。然後，最終添加離子交換水，而準備下述組成之SnAg鍍敷液。此外，甲烷磺酸錫水溶液與甲烷磺酸銀水溶液係分別藉由對金屬Sn板、金屬Ag板在甲烷磺酸水溶液中進行電解而調製。
(SnAg鍍敷液的組成) 甲烷磺酸Sn(作為Sn2+ )：60g/L 甲烷磺酸Ag(作為Ag+ )：1.0g/L 甲烷磺酸(作為游離酸)：120g/L 非離子系界面活性劑C1-6：1g/L 非離子系界面活性劑C2-3：1g/L 鄰苯二酚(作為抗氧化劑)：1g/L 苯甲醛(作為調平劑(D-1))：0.05g/L 甲基丙烯酸甲酯(作為調平劑(D-2))：3g/L 離子交換水：其餘部分
＜實施例6、13及比較例3、8、11＞ 就實施例6、13及比較例3、8、11，作為非離子系界面活性劑(C1)及非離子系界面活性劑(C2)，係使用表1及表2所示性質之界面活性劑，而如表3及表4所示地選定。除此之外係以實施例2同樣的方式，準備實施例6、13及比較例3、8、11之SnAg鍍敷液。
(SnCu鍍敷液的準備) ＜實施例10＞ 在甲烷磺酸錫水溶液中混合作為游離酸之甲烷磺酸、作為抗氧化劑之對苯二酚、作為調平劑(D-1)之苯甲醛及作為調平劑(D-2)之甲基丙烯酸甲酯而使其溶解。進一步添加甲烷磺酸銅液並加以混合。藉由混合而調成均勻的溶液。其次，進一步添加作為界面活性劑之上述No.C2-4之聚氧乙烯與聚氧丙烯的縮合物(質量平均分子量：700、式(2)中之R的碳數：9、聚氧乙烯(EO)基的m數：8、聚氧丙烯(PO)基的n數：3)。然後，最終添加離子交換水，而準備下述組成之SnCu鍍敷液。此外，甲烷磺酸錫水溶液與甲烷磺酸銅水溶液係分別藉由對金屬Sn板、金屬Cu板在甲烷磺酸水溶液中進行電解而調製。
(SnCu鍍敷液的組成) 甲烷磺酸Sn(作為Sn2+ )：80g/L 甲烷磺酸Cu(作為Cu2+ )：0.5g/L 甲烷磺酸(作為游離酸)：150g/L 非離子系界面活性劑C2-4：5g/L 對苯二酚磺酸鉀(作為抗氧化劑)：1g/L 苯甲醛(作為調平劑(D-1))：0.2g/L 甲基丙烯酸甲酯(作為調平劑(D-2))：5g/L 離子交換水：其餘部分
＜比較例6、14＞ 就比較例6、14，作為界面活性劑，係使用表2所示性質之界面活性劑，而如表4所示地選定。除此之外係以實施例10同樣的方式，準備比較例6、14之SnCu鍍敷液。
＜比較試驗及評定＞ 使用準備實施例1～14及比較例1～16此30種的鍍敷液，於通孔內形成錫或錫合金的鍍敷堆積層。接著進行回焊處理而形成凸塊。評定形成凸塊前之通孔內之錫或錫合金的鍍敷堆積層的通孔填充性、凸塊形成後之凸塊的外觀及凸塊的高度不均度(均等性)。將其結果示於表3及表4。
(1)通孔內之錫或錫合金鍍敷堆積層的通孔填充性 使用雷射顯微鏡觀察通孔內的錫或錫合金鍍敷堆積層，量測鍍敷堆積層之最高點至最低點的高度差。高度差超過5μm時係評為「不良」、高度差為5μm以下時則判斷為「良好」，將其示於表3及表4之「通孔填充性」一欄。
(2)通孔內之錫或錫合金鍍敷堆積層的外觀 使用雷射顯微鏡觀察通孔內的錫或錫合金鍍敷堆積層，量測表面粗糙度Ra。鍍敷堆積層的表面粗糙度Ra超過2μm時係評為「不良」、若為2μm以下時則判斷為「良好」，將其示於表3及表4之「鍍敷堆積層的外觀」一欄。
(3)凸塊高度的不均度 使用自動外觀檢查裝置量測基板之凸塊的高度。由測得的凸塊高度算出高度不均度。高度不均度為3以下時係評為「均等」、高度不均度超過3時則判斷為「不均等」，將其結果示於表3及表4之「凸塊的高度不均度」一欄。
(4)空隙的產生難易度 形成以180μm、250μm、360μm之各間距間隔排列且直徑為70μm、90μm、120μm的凸塊(共計2000個)。對該等凸塊拍攝穿透X光影像。目視觀察攝得的影像，觀察到1個以上之相對於凸塊的大小為1%以上之大小的空隙時係評為「NG」、未觀察到空隙時則評為「OK」。將其結果示於表3及表4之「空隙」一欄。
Figure 02_image019
Figure 02_image021
由表4可知，就比較例1，由於EO基數m為2而過少，鍍敷堆積層的外觀不良，且通孔填充性亦不良。凸塊的高度不均度更高達5.3，且觀察到空隙的產生而為NG。
就比較例2，由於R的碳數為16而過多，且EO基數m為3而過少，通孔填充性不良，且鍍敷堆積層的外觀亦不良。凸塊的高度不均度更高達8.1，且觀察到空隙的產生而為NG。
就比較例3，由於EO基數m為4而過少，鍍敷堆積層的外觀不良，且通孔填充性亦不良。再者，雖未觀察到空隙的產生而為OK，但凸塊的高度不均度高達4.3。
就比較例4，由於R的碳數為6而過少，鍍敷堆積層的外觀不良，且通孔填充性亦不良。凸塊的高度不均度更高達3.1，且觀察到空隙的產生而為NG。
就比較例5及11，由於R的碳數各為16而過多，通孔填充性皆不良，且鍍敷堆積層的外觀亦不良。再者，雖均未觀察到空隙的產生而為OK，但凸塊的高度不均度高達3.2及4.1。
就比較例6及12，由於EO基數m各為13而過多，通孔填充性皆良好，但鍍敷堆積層的外觀不良。凸塊的高度不均度更高達4.5及3.3，且均觀察到空隙的產生而為NG。
就比較例7及13，由於R的碳數各為16而過多，且EO基數m皆為15而過多，通孔填充性皆不良，且鍍敷堆積層的外觀亦不良。凸塊的高度不均度更高達6.7及7.5，且均觀察到空隙的產生而為NG。
就比較例8及14，由於EO基數m各為15而過多，且PO基數n皆為4而過多，鍍敷堆積層的外觀皆不良，且通孔填充性亦不良。凸塊的高度不均度更高達8.4及9.8，且均觀察到空隙的產生而為NG。
就比較例9及15，由於R的碳數各為16而過多，且PO基數n各為4而過多，通孔填充性皆不良，且鍍敷堆積層的外觀亦不良。凸塊的高度不均度更高達11.4及13.4，且均觀察到空隙的產生而為NG。
就比較例10及16，由於PO基數n各為4而過多，通孔填充性皆不良，且鍍敷堆積層的外觀亦不良。凸塊的高度不均度更高達9.7及10.1，且均觀察到空隙的產生而為NG。
相對於此，就實施例1～14，由於R的碳數各處於7～13的範圍內、EO基數m處於5～11的範圍內，且PO基數n亦處於0～3的範圍內，通孔填充性皆良好，且鍍敷堆積層的外觀亦良好。而且凸塊的高度不均度處於1.0～2.6的範圍而較小，且均未觀察到空隙的產生而為OK。 [產業上可利用性]
本實施形態之錫或錫合金的鍍敷液可利用於印刷電路基板、可撓式印刷電路基板、半導體積體電路等的電路基板。
1‧‧‧基板 2‧‧‧阻焊劑層 3‧‧‧銅種子層 4‧‧‧乾膜阻劑層 6‧‧‧通孔 7‧‧‧鍍錫堆積層(鍍錫皮膜) 8‧‧‧錫凸塊
圖1(a)為在本實施形態之通孔內形成有鍍敷堆積層之基板的剖面圖；(b)為剝離乾膜及銅種子層並將鍍敷堆積層加熱後之基板的剖面圖。 圖2(a)為表示凸塊徑(通孔徑)不同的圖型且鍍敷堆積層的通孔填充性良好之實例的基板的剖面配置圖；(b)為表示凸塊徑(通孔徑)不同的圖型且鍍敷堆積層的通孔填充性不良之實例的基板的剖面配置圖；(c)為表示在(a)中剝離乾膜及銅種子層，並將鍍敷堆積層加熱後之狀態，且形成之凸塊的高度呈均等之實例的基板的剖面配置圖；(d)為表示在(b)中剝離乾膜及銅種子層，並將鍍敷堆積層加熱後之狀態，且形成之凸塊的高度參差不齊之實例的基板的剖面配置圖。
1‧‧‧基板
2‧‧‧阻焊劑層
4‧‧‧乾膜阻劑層
6‧‧‧通孔
7‧‧‧鍍錫堆積層(鍍錫皮膜)
8‧‧‧錫凸塊

Claims (4)

  1. 一種錫或錫合金鍍敷堆積層的形成方法，其係使用用於對存在具有複數種的通孔徑的通孔的基板進行鍍敷的錫或錫合金鍍敷液，於前述基板上形成錫或錫合金鍍敷堆積層的方法，前述錫或錫合金鍍敷液包含：(A)至少包含亞錫鹽之可溶性鹽；(B)選自有機酸及無機酸的酸或其鹽；(C)界面活性劑；(D)調平劑；及(E)添加劑，其特徵為前述界面活性劑係以下通式(1)所示之化合物(C1)或通式(2)所示之化合物(C2)：
    Figure 108109401-A0305-02-0034-1
     式(1)中，R為碳數7~13之烷基，m為8~11，n為1~3，m與n相異；
    Figure 108109401-A0305-02-0034-2
     式(2)中，R為碳數9~13之烷基，m為6~8，n為2~3，m與n相異。
  2. 如請求項1之錫或錫合金鍍敷堆積層的形成方法，其中前述添加劑係進一步包含選自有別於前述2種界面活性劑(C1,C2)之界面活性劑、抗氧化劑及碳數1~3之醇的2種以上。
  3. 一種凸塊的形成方法，其特徵為對如請求項1或2之方法所形成的錫或錫合金的鍍敷堆積層進行回焊處理來形成凸塊。
  4. 一種電路基板的製造方法，其特徵為使用藉由如請求項3之方法所形成的凸塊來製造電路基板。
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