TWI703239B - 錫或錫合金鍍敷液及凸塊的形成方法 - Google Patents

錫或錫合金鍍敷液及凸塊的形成方法 Download PDF

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TWI703239B
TWI703239B TW108109402A TW108109402A TWI703239B TW I703239 B TWI703239 B TW I703239B TW 108109402 A TW108109402 A TW 108109402A TW 108109402 A TW108109402 A TW 108109402A TW I703239 B TWI703239 B TW I703239B
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Taiwan
Prior art keywords
tin
plating solution
acid
surfactant
bumps
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TW108109402A
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English (en)
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TW201940748A (zh
Inventor
巽康司
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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 TW201940748A publication Critical patent/TW201940748A/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
    • 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
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • 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
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
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Abstract

本發明之錫或錫合金鍍敷液包含：包含亞錫鹽的可溶性鹽(A)、由有機酸及無機酸所選出的酸或其鹽(B)、界面活性劑(C)、亞苄丙酮(D)與溶劑(E)，鍍敷液係用於在基材上形成凸塊直徑不同的圖型，亞苄丙酮(D)之量為0.05g/L～0.2g/L，界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)為10～200，溶劑(E)相對於亞苄丙酮(D)之質量比(E/D)為10以上。

Description

錫或錫合金鍍敷液及凸塊的形成方法
本發明關於用於藉由電鍍法形成錫或錫合金的鍍敷膜之錫或錫合金鍍敷液，及使用其之凸塊的形成方法。更詳細而言，關於包含亞苄丙酮之錫或錫合金鍍敷液及使用其之凸塊的形成方法，該錫或錫合金鍍敷液適合於在半導體晶圓等的基材上形成凸塊直徑不同的焊料凸塊。 本申請案係以2018年3月20日在日本申請的特願2018-52012號、2018年3月26日在日本申請的特願2018-57551號及2019年3月6日在日本申請的特願2019-40216號為基礎，主張優先權，在此援用其內容。
專利文獻1中揭示以下之事項。以往，於如半導體晶片搭載用基板之基材中，形成縱橫比等為特定的構造之通孔。有揭示於該構造之通孔，使用組合有如亞苄丙酮的特定填充用有機化合物(C)與非離子系界面活性劑(D)之錫或錫合金鍍敷浴，藉由電鍍方式進行通孔填充，而形成突起電極之方法。依照該方法，於基材上之通孔，藉由錫或錫合金的電鍍而形成突起電極時，藉由成分(C)與成分(D)之共存，而有效果地抑制金屬析出至通孔上部，使從通孔底部優先地進行金屬之析出。藉此，無空隙之發生，可圓滑地填充通孔。
又，專利文獻2中揭示一種水性的酸性錫、鉛或錫・鉛合金之電鍍浴，其包含：(a)選自由烷磺酸的二價錫鹽、烷磺酸的二價鉛鹽以及烷磺酸的二價錫鹽及烷磺酸的二價鉛鹽之混合物所成之群組的浴可溶性金屬鹽；(b)烷磺酸；(c)如α-萘甲醛及亞苄基丙酮(亞苄丙酮)之混合物的光澤劑；(d)於丙二醇中包含聚矽氧與二氧化矽及/或矽酸鹽之混合物的消泡劑；(e)由乙氧基化芳基苯酚所成的第一非離子性界面活性劑；及(f)由乙氧基化短鏈醇所成的第二非離子性界面活性劑。而且，顯示作為上述光澤劑的α-萘甲醛係以約0.02g/L～約5g/L之濃度存在，亞苄基丙酮(亞苄丙酮)係以約0.02g/L～約5g/L之濃度存在。藉由該電鍍浴，甚至連在藉由浴的高電流密度及/或激烈的循環而發生的高速鍍敷條件下，也都具有在電鍍中幾乎或完全不發泡的固有能力。而且，該浴係被認為生成均勻且優異的錫及/或鉛之析出物。
再者，專利文獻3中揭示一種pH未達約3.0的水性酸性錫、鉛或錫・鉛合金之電鍍浴，其包含：選自由錫離子、鉛離子及彼等的混合離子所組成之群組的金屬離子為約15.0g/L～約350.0g/L；選自由氟硼酸鹽、氟矽酸鹽、胺磺酸鹽及彼等的混合鹽所組成之群組的自由基為約100.0g/L～約500.0g/L；及，烷氧基化的脂肪酸之特定烷基烯丙基界面活性劑為約10.0g/L～約25.0g/L。該電鍍浴進一步以約0.1g/L～約10.0g/L之量包含選自由亞苄基丙酮(亞苄丙酮)、3-丁基醛、噻吩甲醛、甲苯甲醛、桂皮醛及大茴香醛所組成之群組之含羰基的化合物。藉由該電鍍浴，可提供一種簡潔且有效率的電鍍程序，其堆積具有充分光澤的錫・鉛合金鍍層。藉此，可以經濟的條件製造具有充分的光澤之錫・鉛合金，可提供經錫・鉛合金所電鍍之具有光澤的外觀之製品。
近年來，於一個晶圓基板等之基材上，凸塊直徑或凸塊間距不同的配線圖型變成可混合存在。於如此複雜的圖型中，尤其要求以均一高度形成不同凸塊直徑的凸塊。依照上述專利文獻1～3之鍍敷浴，具有優異的特點為：可在不發生空隙下圓滑地填充通孔，或在電鍍中可在不發泡下生成均勻的析出物，或簡潔且經濟地製造具有充分光澤的製品等。然而，此等之專利文獻1～3中的鍍敷液之課題不是在於：在一個基材上形成凸塊直徑不同(以下亦稱為「異徑」)的凸塊時，謀求凸塊直徑不同的凸塊間之高度的均一性(以下亦稱為「凸塊的高度均一性」)。
具體而言，藉由圖2說明以凸塊直徑不同的圖型來形成凸塊之例，如圖2(a)所示，首先在如半導體晶圓基板之基材1的表面上，依順序形成鈦層2及銅種子層3。其次，形成阻劑層4，對於該阻劑層4 進行遮罩曝光、顯像，形成具有不同直徑的通孔4a、4b之阻劑圖型5。接著，於此等之通孔4a、4b內的銅種子層3上鍍敷銅或鎳，形成基底層6。隨後，藉由使用錫鍍敷液，通過銅種子層3供電，而在阻劑圖型5的通孔4a、4b之內部進行電鍍錫，於基底層6之上的通孔4a、4b內分別形成錫鍍敷堆積層(錫鍍敷膜)7a、7b。接著如圖2(b)所示，依順序去除阻劑層4、銅種子層3及鈦層2。接著，藉由回焊處理而熔融殘留的錫鍍敷堆積層7a、7b。藉此，如圖2(c)所示，形成錫凸塊8a、8b。於此等之錫凸塊中，凸塊直徑大的凸塊8b之高度係比凸塊直徑小的凸塊8a之高度更大，發生高度的差異D，無法謀求凸塊的高度均一化(提高凸塊的高度均一性)。
縱然使用專利文獻1～3所示的習知含有亞苄丙酮的鍍敷液進行電鍍，也難以謀求凸塊的高度均一化(提高凸塊的高度均一性)。
再者，本說明書中所謂之凸塊直徑不同的圖型，即「異徑圖型」，就是指最小的基底層面積Smin與最大的基底層面積Smax之比(Smax/Smin)為1.5以上之圖型。於習知的鍍敷液中，當Smax/Smin為1.5以上時，難以抑制異徑凸塊的高度偏差。Smax/Smin之上限值雖然沒有特別的限制，但約30。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2016-74963號公報 [專利文獻2]日本特公平3-17912號公報 [專利文獻3]美國發明專利第3,730,853號公報
[發明所欲解決的課題]
本發明之目的在於提供錫或錫合金鍍敷液及使用其之凸塊的形成方法，該錫或錫合金鍍敷液係即使凸塊直徑不同的圖型，也回焊後所形成的大徑及小徑之凸塊的高度偏差小，具有凸塊高度的均一性，且得到無空隙之凸塊。 [解決課題的手段]
本發明之第1態樣的錫或錫合金鍍敷液包含：至少包含亞錫鹽的可溶性鹽(A)、由有機酸及無機酸所選出的酸或其鹽(B)、界面活性劑(C)、亞苄丙酮(D)與溶劑(E)，該錫或錫合金鍍敷液係用於在基材上形成凸塊直徑不同的圖型，前述亞苄丙酮(D)係在前述鍍敷液中以0.05g/L～0.2g/L之量含有，前述界面活性劑(C)相對於前述亞苄丙酮(D)之質量比(C/D)為10～200，前述溶劑(E)相對於前述亞苄丙酮(D)之質量比(E/D)為10以上。
本發明之第2態樣係在第1態樣之錫或錫合金鍍敷液中，前述界面活性劑(C)為聚氧乙烯(EO)與聚氧丙烯(PO)縮合成的非離子系界面活性劑，或由苯酚、烷基苯酚、苯乙烯化苯酚、β-萘酚、雙酚類及異丙苯基苯酚所選出的任一者與聚氧乙烯(EO)縮合成的非離子系界面活性劑。
本發明之第3態樣之凸塊的形成方法具有：使用第1或第2態樣之錫或錫合金鍍敷液，在基材上形成不同直徑之複數的錫或錫合金鍍敷堆積層之步驟，及接著進行回焊處理，形成凸塊直徑不同之複數的凸塊之步驟。 [發明的效果]
於本發明之第1態樣之錫或錫合金鍍敷液中，亞苄丙酮(D)係在鍍敷液中以0.05g/L～0.2g/L之量含有。界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)係規定為10～200。又，溶劑(E)相對於亞苄丙酮(D)之質量比(E/D)係規定為10以上。如圖1(a)所示，若藉由使用該鍍敷液，通過銅種子層13供電，在阻劑圖型15之通孔內部進行電鍍錫，則鍍敷液中的亞苄丙酮係吸附於通孔之底部，阻礙錫之析出。於鍍敷液容易進入的大徑之通孔14b中，亞苄丙酮容易吸附，抑制錫之析出的效果大。相對於其，於鍍敷液難進入的小徑之通孔14a中，相較於大徑之通孔14b，亞苄丙酮之吸附量相對地少，抑制錫之析出的效果小。因此，大徑之通孔14b的鍍敷堆積層17b之膜厚係比小徑之通孔14a的鍍敷堆積層17a之膜厚更薄地形成。如圖1(b)所示，若依順序去除阻劑層14、種子層13、12，接著藉由回焊處理而熔融殘留的鍍敷堆積層17a、17b，則如圖1(c)所示，形成凸塊高度之偏差少且無空隙之錫凸塊(鍍敷膜)18a、18b。藉此，可得到複數的焊料凸塊之高度偏差為10%以下之附焊料凸塊的電子零件，其具備：基板、形成在基板上之複數的各自面積不同的基底層、及形成在複數的基底層上各自之複數的焊料凸塊。
於本發明之第2態樣之錫或錫合金鍍敷液中，界面活性劑(C)係吸附於鍍敷膜之表面，抑制錫之結晶成長，將結晶微細化。藉此，得到鍍敷膜的外觀改良、鍍敷膜與被鍍敷物的密著性升高、膜厚的均一化等作用，與亞苄丙酮(D)相乘地更有效果地發揮上述效果。
於本發明之第3態樣之凸塊的形成方法中，使用第1觀點或第2觀點之錫或錫合金鍍敷液，在基材上形成不同直徑的錫或錫合金鍍敷堆積層。接著，進行回焊處理。藉此，即使凸塊直徑不同的圖型，也能形成高度均一且無空隙的凸塊。
依照本發明之第1～3態樣，可提供一種電子零件，其係在基材上具有擁有凸塊高度均一性的異徑凸塊。若使用該電子零件，則可製作無電連接不良之可靠性高的半導體裝置。
[實施發明的形態]
接著，說明實施本發明之形態。
本實施形態之錫或錫合金鍍敷液包含：至少包含亞錫鹽的可溶性鹽(A)、由有機酸及無機酸所選出的酸或其鹽(B)、界面活性劑(C)、亞苄丙酮(D)與溶劑(E)。其特徵之點為：鍍敷液係用於在基材上形成凸塊直徑不同的圖型，亞苄丙酮(D)係在鍍敷液中以0.05g/L～0.2g/L之量含有，界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)為10～200，溶劑(E)相對於亞苄丙酮(D)質量比(E/D)為10以上。再者，本實施形態之基材包含半導體晶圓及半導體晶片搭載用之基板。
本實施形態之錫合金係錫與選自銀、銅、鉍、鎳、銻、銦及鋅的1種或2種以上的金屬之合金。例如，可舉出錫-銀合金、錫-銅合金、錫-鉍合金、錫-鎳合金、錫-銻合金、錫-銦合金及錫-鋅合金等之2元合金，或錫-銅-鉍及錫-銅-銀合金等之3元合金。
[至少包含亞錫鹽的可溶性鹽(A)] 本實施形態之可溶性鹽(A)係由亞錫鹽與選自由該亞錫鹽及銀、銅、鉍、鎳、銻、銦、鋅所組成之群組的1種或2種以上的金屬之鹽的混合物之任一者所構成。
因此，本實施形態之可溶性鹽(A)係意指在鍍敷液中生成Sn2+ 、Ag+ 、Cu+ 、Cu2+ 、Bi3 +、Ni2+ 、Sb3+ 、In3+ 、Zn2+ 等的各種金屬離子之任意的可溶性鹽。作為可溶性鹽，例如可舉出此等金屬的氧化物、鹵化物、無機酸或有機酸之金屬鹽等。
作為金屬氧化物，可舉出氧化亞錫、氧化銀、氧化銅、氧化鎳、氧化鉍、氧化銻、氧化銦、氧化鋅等。 作為金屬之鹵化物，可舉出氯化亞錫、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之金屬鹽，可舉出硫酸銅、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、醋酸銅、醋酸鎳、碳酸鎳、錫酸鈉、硼氟酸亞錫、甲磺酸亞錫、甲磺酸銀、甲磺酸銅、甲磺酸鉍、甲磺酸鎳、偏磺酸銦、雙甲磺酸鋅、乙磺酸亞錫、2-羥基丙磺酸鉍等。
[由有機酸及無機酸所選出的酸或其鹽(B)] 本實施形態之酸或其鹽(B)係由有機酸、無機酸及彼等之鹽所選出。 於有機酸中，可舉出烷磺酸、烷醇磺酸、芳香族磺酸等之有機磺酸或脂肪族羧酸等。 於無機酸中，可舉出氟硼酸、氟矽酸、胺磺酸、鹽酸、硫酸、硝酸、過氯酸等。 彼等之鹽為鹼金屬之鹽、鹼土類金屬之鹽、銨鹽、胺鹽、磺酸鹽等。 作為成分(B)，從金屬鹽的溶解性或排水處理的容易性之觀點來看，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，可舉出甲磺酸、乙磺酸、1-丙磺酸、2-丙磺酸、1-丁磺酸、2-丁磺酸、戊磺酸、己磺酸、癸磺酸、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，可舉出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、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。具體而言，可舉出1-萘磺酸、2-萘磺酸、甲苯磺酸、二甲苯磺酸、對苯酚磺酸、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，例如可舉出乙酸、丙酸、丁酸、檸檬酸、酒石酸、葡萄糖酸、磺基琥珀酸、三氟乙酸等。
[界面活性劑(C)] 本實施形態之界面活性劑(C)具有與亞苄丙酮(D)相乘而提高能抑制錫的析出之效果的作用。作為該界面活性劑(C)，較佳為聚氧乙烯(EO)與聚氧丙烯(PO)縮合成的非離子系界面活性劑，或由苯酚、烷基苯酚、苯乙烯化苯酚、β-萘酚、雙酚類及異丙苯基苯酚所選出的任一者與聚氧乙烯(EO)縮合成的非離子系界面活性劑。 作為EOPO縮合物(聚氧乙烯(EO)與聚氧丙烯(PO)縮合成的縮合物)，具體而言，較佳為以下述式(1)所示的N,N-二聚環氧烷N-烷基胺。此N,N-二聚環氧烷N-烷基胺具有1個碳原子數在5個以上20個以下之範圍中的烷基(R)，具有2個以莫耳比(EO基：PO基)表示，環氧乙烷基(EO基)與環氧丙烷基(PO基)各自獨立地以30：70～70：30之範圍含有的聚環氧烷基(X及Y)。 EO基為親水性，PO基為疏水性。藉此，N,N-二聚環氧烷N-烷基胺的水溶性與向錫或錫合金之表面的吸附性係平衡良好地發揮。即，於本實施形態之鍍敷液中，EO基與PO基之比率在上述之範圍，由於平衡良好地具有EO基與PO基之兩者，非離子系界面活性劑對於錫或錫合金的親和性高，容易吸附於鍍敷膜之表面。藉由複數的界面活性劑分子吸附於鍍敷膜之表面，而形成層狀的皮膜，抑制金屬之析出反應。因此，茲認為藉由該界面活性劑，鍍敷膜厚變更均勻。 N,N-二聚環氧烷N-烷基胺係其質量平均分子量較佳在500以上30000以下之範圍。質量平均分子量過小時，有抑制錫或錫合金之析出的效果不充分之虞。另一方面，質量平均分子量過大時，抑制力變過強，有不形成均勻的鍍敷膜之虞。此N,N-二聚環氧烷N-烷基胺係可單獨使用1種，也可組合2種以上使用。 本實施形態之鍍敷液中的N,N-二聚環氧烷N-烷基胺之含量較佳為0.1g/L以上100g/L以下之範圍，更佳為1g/L以上50g/L以下之範圍。若N,N-二聚環氧烷N-烷基胺之含量過度地少或多，則有不形成均勻的鍍敷膜之虞。
Figure 02_image001
作為苯酚與聚氧乙烯(EO)縮合成的非離子系界面活性劑，可舉出聚氧乙烯苯基醚。 作為烷基苯酚與聚氧乙烯(EO)縮合成非離子系界面活性劑，可舉出聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚氧乙烯十二基苯基醚。 作為苯乙烯化苯酚與聚氧乙烯(EO)縮合成的非離子系界面活性劑，可舉出聚氧乙烯單苯乙烯化苯基醚、聚氧乙烯二苯乙烯化苯基醚、聚氧乙烯三苯乙烯化苯基醚。 作為β-萘酚與聚氧乙烯(EO)縮合成的非離子系界面活性劑，可舉出聚氧乙烯β-萘基醚。 作為雙酚類與聚氧乙烯(EO)縮合成非離子系界面活性劑，可舉出聚氧乙烯雙酚A醚、聚氧乙烯雙酚E醚、聚氧乙烯雙酚F醚、聚氧乙烯雙酚S醚、聚氧乙烯雙酚M醚。 作為異丙苯基苯酚與聚氧乙烯(EO)縮合成非離子系界面活性劑，可舉出聚氧乙烯異丙苯基苯基醚。 此等之非離子系界面活性劑的質量平均分子量較佳在100以上5000以下之範圍。質量平均分子量過小時，有抑制錫或錫合金之析出的效果不充分之虞。另一方面，質量平均分子量過大時，抑制力變過強，有不形成均勻的鍍敷膜之虞。
作為本實施形態之界面活性劑(C)，代替上述界面活性劑，亦可單獨使用其他的界面活性劑。或者，也可併用其他的界面活性劑與上述界面活性劑。作為此時之其他的界面活性劑，可舉出通常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，可舉出聚氧乙烯(環氧乙烷：含有12莫耳)壬基醚硫酸鈉等之聚氧化烯烷基醚硫酸鹽；聚氧乙烯(環氧乙烷：含有12莫耳)十二基苯基醚硫酸鈉等之聚氧化烯烷基苯基醚硫酸鹽；十二基苯磺酸鈉等之烷基苯磺酸鹽；1-萘酚-4-磺酸鈉、2-萘酚-3,6-二磺酸二鈉等之萘酚磺酸鹽；二異丙基萘磺酸鈉、二丁基萘磺酸鈉等之(多)烷基萘磺酸鹽；十二基硫酸鈉、油基硫酸鈉等之烷基硫酸鹽等。
作為陽離子系界面活性劑，可舉出單～三烷基胺鹽、二甲基二烷基銨鹽、三甲基烷基銨鹽、十二基三甲基銨鹽、十六基三甲基銨鹽、十八基三甲基銨鹽、十二基二甲基銨鹽、十八烯基二甲基乙基銨鹽、十二基二甲基苄基銨鹽、十六基二甲基苄基銨鹽、十八基二甲基苄基銨鹽、三甲基苄基銨鹽、三乙基苄基銨鹽、十六基吡啶鎓鹽、十二基吡啶鎓鹽、十二基甲基吡啶鎓鹽、十二基咪唑啉鎓鹽、油基咪唑啉鎓鹽、十八基胺乙酸鹽、十二基胺乙酸鹽等。
作為上述非離子系界面活性劑以外的非離子系界面活性劑，可舉出直鏈烷基聚氧乙烯醚、分支烷基聚氧乙烯醚、烷基苯酚聚氧乙烯醚、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及彼等的硫酸化或磺化加成物等。
作為兩性界面活性劑，可舉出甜菜鹼、羧基甜菜鹼、咪唑啉鎓甜菜鹼、磺基甜菜鹼、胺基羧酸等。
[亞苄丙酮(D)] 本實施形態之亞苄丙酮(D)係可直接使用市售者。又，可使用將市售者精製而去除雜質後的精製品。 亞苄丙酮(D)係吸附於被鍍敷物之表面，阻離因電析所致的錫之結晶成長，故具有能抑制鍍敷皮膜的堆積之效果。 而且，亞苄丙酮係容易吸附於鍍敷液容易進入的大徑之通孔，鍍敷的抑制效果大。相對於其，亞苄丙酮係難以吸附於鍍敷液難以進入的小徑之通孔，鍍敷的抑制效果小。 因此，與小徑之通孔的鍍敷堆積層之形成比較下，大徑之通孔的鍍敷堆積層之形成係更被抑制。因此，大徑之通孔的鍍敷膜係比小徑之通孔的鍍敷膜更薄地形成。藉由回焊處理而熔融如此的鍍敷膜，可得到高度無偏差的凸塊。 再者，亞苄丙酮之含量較佳為按照異徑凸塊的直徑差異之大小而調整。具體而言，異徑凸塊的直徑差異愈大，較佳為愈增多亞苄丙酮的摻合量。
[溶劑(E)] 作為本實施形態之溶劑(E)，較佳為碳數1～3的醇。碳數1～3的醇係使上述界面活性劑或亞苄丙酮的溶解性升高。作為該醇，可舉出甲醇、乙醇、1-丙醇、2-丙醇(異丙醇)等。醇係可單獨使用1種，也可組合2種以上使用。
[錫或錫合金鍍敷液之製造] 本實施形態之錫或錫合金鍍敷液係可藉由混合上述可溶性錫鹽(A)、由有機酸及無機酸所選出的酸或其鹽(B)、界面活性劑(C)、亞苄丙酮(D)、溶劑(E)與水(剩餘部分)而調製。
於此，亞苄丙酮(D)係以在鍍敷液中成為0.05g/L～0.2g/L之濃度，較佳成為0.06g/L～0.18g/L，更佳成為0.08g/L～0.15g/L之濃度的方式添加。不同大小的通孔徑之差異愈大，在上述範圍內愈多地添加。未達0.05g/L時，上述亞苄丙酮的效果低，無法減小回焊後的異徑凸塊之高度的偏差。超過0.2g/L時，亞苄丙酮過度地吸附於通孔之底部，因鍍敷皮膜表面粗面化而變成黑色(發生一般稱為焦化・燒傷的現象)，發生鍍敷皮膜的外觀不良。
又，以界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)成為10～200，較佳成為30～180，更佳成為50～150之方式，混合界面活性劑與亞苄丙酮。質量比C/D未達10或超過200時，無法充分發揮藉由亞苄丙酮與界面活性劑之相乘效果而抑制錫的析出之作用，抑制大徑凸塊中之錫的析出之作用變弱。因此，無法減小回焊後的異徑凸塊之高度的偏差。
又，界面活性劑(C)在鍍敷液中之濃度較佳為5g/L～20g/L。若界面活性劑(C)之量過度地少或多，則有不形成均勻的鍍敷膜之虞。更佳宜為5～10g/L。
再者，以溶劑(E)相對於亞苄丙酮(D)之質量比(E/D)成為10以上，較佳成為20以上，更佳成為30以上之方式，混合溶劑與亞苄丙酮。質量比E/D未達10時，必需量的亞苄丙酮不溶解於溶劑中，無法作成鍍敷液。質量比E/D之上限係沒有特別的限定，但宜為300以下。超過300時，變成使用超出需要的溶劑，有鍍敷液的成本上升之虞。又，溶劑(E)在鍍敷液中之濃度較佳為0.5g/L～20g/L。未達0.5g/L時，在鍍敷液中亞苄丙酮(D)析出，無法減小回焊後的異徑凸塊之高度的偏差。超過20g/L時，有鍍敷液的成本上升之虞。更佳宜為0.5～10g/L。
又，作為上述之可溶性金屬鹽(A)，可單獨使用1種，或也可使用2種以上的混合物。鍍敷液中的可溶性金屬鹽(A)之含量為10～200g/L，較佳為50～100g/L。若含量為適當範圍外，則得不到表面平滑且膜厚均勻性良好之鍍敷皮膜。
作為無機酸、有機酸或其鹽(B)，可單獨使用1種，或也可使用2種以上的混合物。鍍敷液中的無機酸、有機酸或其鹽(B)之含量為10～300g/L，較佳為100～200g/L。若含量為適當範圍外，則得不到表面平滑且膜厚均勻性良好之鍍敷皮膜。
[凸塊之形成方法] 說明使用本實施形態之鍍敷液來形成凸塊之方法。如圖1(a)所示，首先於導體晶圓基板等的基材11之表面，依順序形成鈦層12及銅種子層13。例如，鈦層12係藉由濺鍍法形成厚度100nm左右，銅種子層13係藉由濺鍍法形成厚度500nm左右。然後，形成特定厚度的阻劑層14。對於該阻劑層14進行遮罩曝光、顯像，形成具有不同直徑的通孔14a、14b之阻劑圖型15。接著，於此等通孔14a、14b內之銅種子層13上鍍敷銅或鎳，形成基底層16。接著，使用上述本實施形態之錫或錫合金鍍敷液，藉由通過銅種子層13供電，在阻劑圖型15之通孔14a、14b的內部進行電鍍錫。藉此，於基底層16之上的通孔14a、14b內，分別形成錫或錫合金之鍍敷堆積層(錫或錫合金之鍍敷膜)17a、17b。接著，如圖1(b)所示，使用有機溶劑，剝離阻劑層14。接著，藉由酸依順序去除銅種子層13及鈦層12。更繼續，藉由將殘留的錫或錫合金之鍍敷堆積層(錫或錫合金之鍍敷膜)17a、17b在氮氣環境下，在210℃～240℃回焊處理而熔融。藉此，如圖1(c)所示，形成圓頂形狀的錫或錫合金之凸塊18a、18b。再者，錫或錫合金之凸塊係不限於俯視為圓形的圓柱狀凸塊，包含俯視為三角形、四角形、多角形的角柱狀凸塊及俯視為橢圓形的橢圓柱狀凸塊。
此處，電鍍係在鍍敷膜的形成時之電流密度為0.1A/dm2 以上100A/dm2 以下之範圍，較佳為0.5A/dm2 以上20A/dm2 以下之範圍內進行。若電流密度過低，則生產性變差，若過高則凸塊的高度均一性變差。液溫為10℃以上50℃以下之範圍，較佳為20℃以上40℃以下之範圍。 再者，雖然未圖示，但是於上述凸塊的形成方法中，亦可形成基底層，接著剝離阻劑層14，形成另一新的阻劑層，以與基底層的直徑相同之方式，將該阻劑層予以遮罩曝光，進行顯像，形成具有不同直徑的通孔14a、14b之阻劑圖型15。 [實施例]
接著，詳細說明本發明之實施例連同比較例。
(Sn鍍敷液的準備) ＜實施例1＞ 首先，使用亞苄丙酮(D)與甲醇(E)，以質量比計E/D成為10之方式混合，將亞苄丙酮溶解於甲醇中。其次，於甲磺酸Sn(A)之水溶液中，混合作為游離酸的甲磺酸(B)與亞苄丙酮的甲醇溶液，得到均勻的溶液。接著，作為界面活性劑(C)，準備上述式(1)之N,N-二聚環氧烷N-烷基胺。該N,N-二聚環氧烷N-烷基胺具有1個碳原子數12個的烷基(R)，具有2個EO基：PO基為50：50的莫耳比之含有EO基與PO基的聚環氧烷基(X及Y)。以質量比表示，C/D成為100之方式，添加該界面活性劑。再者，該界面活性劑的烷基之碳數為12，質量平均分子量為940。而且，最後添加離子交換水，準備下述組成的Sn鍍敷液。 再者，甲磺酸Sn水溶液係藉由在甲磺酸水溶液中電解金屬Sn板而調製。又，鍍敷液中的醇量係藉由氣相層析法測定，確認調配量為大致相同的含量。
(Sn鍍敷液之組成) 甲磺酸Sn(當作Sn2+ )：80g/L 甲磺酸(當作游離酸)：150g/L 非離子系界面活性劑：5g/L 亞苄丙酮：0.05g/L 甲醇：0.5g/L 離子交換水：剩餘部分
表1中顯示實施例1之鍍敷液中的成分(A)～(E)之種類與調配比例，表4中顯示質量比(C/D)及質量比(E/D)。
Figure 02_image003
Figure 02_image005
Figure 02_image007
Figure 02_image009
＜實施例2～17及比較例1～5＞ 將實施例2～11及比較例1～5之鍍敷液中的成分(A)～(E)之種類與調配比例變更為如表1、3所示，將質量比(C/D)及質量比(E/D)變更為如表4所示。其以外係與實施例1同樣地，準備鍍敷液。於實施例6中，使用甲磺酸Sn、甲磺酸Ag及甲磺酸Cu作為可溶性鹽，準備SnAgCu鍍敷液。 將實施例12～17之鍍敷液中的成分(A)～(E)之種類與調配比例變更為如表2所示，將質量比(C/D)及質量比(E/D)變更為如表4所示。其以外係與實施例1同樣地，準備鍍敷液。於實施例12～17中，使用表2所示的界面活性劑(C)。於實施例13中，使用甲磺酸Sn、甲磺酸Ag作為可溶性鹽，準備SnAg鍍敷液。 再者，表1～3中，「MeOH」意指甲醇，「IPA」意指異丙醇。
＜比較試驗及評價＞ 使用實施例1～17及比較例1～5之22種類準備的鍍敷液，如圖1(a)～(c)所示，於22種類的矽晶圓上，在液溫25℃、電流密度4A/dm2 之條件下進行電鍍。藉此，在俯視各自為圓形的小徑之通孔及大徑之通孔的內部之基底層上形成鍍敷膜。然後，依順序去除阻劑層、銅種子層及鈦層。接著，藉由將殘留的鍍敷膜在氮氣環境氣下，在240℃回焊處理而熔融。藉此，形成2000個直徑約20μm的小徑之凸塊，形成2000個直徑約60μm的大徑之凸塊。用以下之方法評價(1)回焊處理後之凸塊的高度偏差(均一性)及(2)凸塊表面的鍍敷膜之外觀。上述之表4中顯示其結果。
(1)凸塊的高度偏差(均一性) 將從基底層之表面起到圓頂形狀的凸塊之頭頂部為止的距離當作回焊處理後之凸塊的高度。對於2000個小徑之凸塊與2000個大徑之凸塊的合計4000個，使用雷射顯微鏡測定各自之凸塊的高度。求得4000個凸塊的高度之平均值、最大值及最小值，藉由下述之式算出凸塊的高度偏差。 凸塊高度偏差(%)={(最大值-最小值)/平均值}×100
(2)凸塊表面的鍍敷膜之外觀 將22種類準備的錫及錫合金鍍敷液各自分別地置入山本鍍金試驗器公司製的赫耳電池槽中。在液中配置銅製赫耳電池板作為陰極，配置白金板作為陽極，進行赫耳電池試驗。作為鍍敷條件，將液溫設為25℃，將通電電流設為3A，鍍敷處理時間係設為5分鐘。於鍍敷處理中，以陰極搖臂攪拌鍍敷液。用以下之程序進行赫耳電池評價。使用電流密度一覽板，目視確認經鍍敷處理的赫耳電池板上之鍍敷膜的皮膜外觀。將光澤・半光澤的皮膜評價為「良好」。將無光澤・混濁的皮膜評價「可」。將焦化・燒傷的皮膜評價為「不良」。用以上的3個判斷基準進行評價。
如由表4可明知，於比較例1中，鍍敷膜之外觀為「可」。但是，由於亞苄丙酮在鍍敷液中的含有比例為0.01g/L之過少，故回焊處理後的凸塊之高度偏差為16.2%之大，凸塊的高度均一性差。
於比較例2中，回焊處理後的凸塊之高度偏差為7.1%之小，具有凸塊的高度均一性。但是，由於亞苄丙酮在鍍敷液中的含有比例為0.3/L之過剩，故鍍敷膜之外觀為「不良」。
於比較例3中，鍍敷膜之外觀為「可」。但是，由於界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)為5之過小，故回焊處理後的凸塊之高度偏差為12.8%之大，凸塊的高度均一性差。
於比較例4中，鍍敷膜之外觀為「可」。但是，由於界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)為250之過大，故回焊處理後的凸塊之高度偏差為21.5%之大，凸塊的高度均一性差。
於比較例5中，由於溶劑(E)相對於亞苄丙酮(D)之質量比(E/D)為5之過小，故亞苄丙酮不溶於溶劑的甲醇中。因此，回焊處理後的凸塊之高度偏差與鍍敷膜之外觀之評價皆無法完成。
相對於其，如由表4可明知，於實施例1～17中，亞苄丙酮(D)在鍍敷液中之含有比例、界面活性劑(C)相對於亞苄丙酮(D)之質量比(C/D)及溶劑(E)相對於亞苄丙酮(D)之質量比(E/D)皆滿足本實施形態之要件。因此，回焊處理後的凸塊之高度偏差為1.8～8.6之小，且鍍敷膜之外觀為「良好」或「可」。 [產業上的利用可能性]
本實施形態之錫或錫合金鍍敷液係可利用於半導體晶圓基板、印刷電路基板、可撓性印刷電路基板、半導體積體電路等之電路基板。
11‧‧‧基材 12‧‧‧鈦層 13‧‧‧銅種子層 14‧‧‧阻劑層 14a、14b‧‧‧通孔 15‧‧‧阻劑圖型 16‧‧‧基底層 17a、17b‧‧‧錫或錫合金鍍敷堆積層(錫或錫合金鍍敷膜) 18a、18b‧‧‧錫凸塊
圖1係顯示本實施形態中，將凸塊形成凸塊直徑不同的圖型之步驟之圖。圖1(a)顯示在通孔內形成有不同直徑的鍍敷堆積層之剖面圖。圖1(b)顯示剝離阻劑層、鈦層及銅種子層後之不同直徑的鍍敷堆積層之剖面圖。圖1(c)顯示回焊處理後之均一形成凸塊的高度之不同直徑的凸塊之剖面圖。 圖2係顯示習知技術中，將凸塊形成凸塊直徑不同的圖型之步驟之圖。圖2(a)顯示在通孔內形成有不同直徑的鍍敷堆積層之剖面圖。圖2(b)顯示剝離阻劑層、鈦層及銅種子層後之不同直徑的鍍敷堆積層之剖面圖。圖2(c)顯示回焊處理後之不均一形成凸塊的高度之不同直徑的凸塊之剖面圖。
11‧‧‧基材
12‧‧‧鈦層
13‧‧‧銅種子層
14‧‧‧阻劑層
14a、14b‧‧‧通孔
15‧‧‧阻劑圖型
16‧‧‧基底層
17a、17b‧‧‧錫或錫合金鍍敷堆積層(錫或錫合金鍍敷膜)
18a、18b‧‧‧錫凸塊

Claims (3)

  1. 一種錫或錫合金鍍敷液，其包含：至少包含亞錫鹽的可溶性鹽(A)、由有機酸及無機酸所選出的酸或其鹽(B)、界面活性劑(C)、亞苄丙酮(D)與溶劑(E)，其特徵為：前述鍍敷液係用於在基材上形成凸塊直徑不同的圖型，前述亞苄丙酮(D)係在前述鍍敷液中以0.1g/L~0.2g/L之量含有，前述溶劑(E)係在前述鍍敷液中以5g/L~10g/L之量含有，前述界面活性劑(C)相對於前述亞苄丙酮(D)之質量比(C/D)為50~200，前述溶劑(E)相對於前述亞苄丙酮(D)之質量比(E/D)為50~100。
  2. 如請求項1之錫或錫合金鍍敷液，其中前述界面活性劑(C)係聚氧乙烯(EO)與聚氧丙烯(PO)縮合成的非離子系界面活性劑，或由苯酚、烷基苯酚、苯乙烯化苯酚、β-萘酚、雙酚類及異丙苯基苯酚所選出的任一者與聚氧乙烯(EO)縮合成的非離子系界面活性劑。
  3. 一種凸塊的形成方法，其具有：使用如請求項1或2之錫或錫合金鍍敷液，在基材上形成不同直徑之複數的錫或 錫合金鍍敷堆積層之步驟，及接著進行回焊處理，形成凸塊直徑不同之複數的凸塊之步驟。
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