TW201400646A - 鍍覆浴及方法 - Google Patents
鍍覆浴及方法 Download PDFInfo
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- TW201400646A TW201400646A TW102111360A TW102111360A TW201400646A TW 201400646 A TW201400646 A TW 201400646A TW 102111360 A TW102111360 A TW 102111360A TW 102111360 A TW102111360 A TW 102111360A TW 201400646 A TW201400646 A TW 201400646A
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- silver
- alkyl
- tin
- acid
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- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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- C25D3/00—Electroplating: Baths therefor
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Abstract
本發明係揭露具有某些硫化物化合物之銀電鍍浴及使用這些電鍍浴電沉積含銀層之方法。此等電鍍浴有用於提供具有減少孔洞形成及改良晶粒內均勻度之含銀焊料沉積物。
Description
本發明大體而言係有關電解金屬鍍覆之領域。尤其,本發明係有關電解錫-合金鍍覆之領域。
金屬及金屬-合金具有商業上的重要性,特別是在電子產業上,其經常使用作為電氣接點、最終精加工件及焊料。曾經是最常見的錫-合金焊料之錫-鉛的使用,由於對鉛的限制逐漸增加而已衰退。通常以無鉛合金,如錫-銀,錫-銅,錫-鉍,錫-銀-銅,及其他者取代錫-鉛焊料。這些焊料經常使用鍍覆浴,如電鍍浴而沉積在基板上。
以金屬塗佈物電鍍物件之方法通常係涉及使電流通過在鍍覆溶液中之兩個電極間,其中一個電極(通常為陰極)為欲鍍覆之物件。典型的銀或銀-合金鍍覆溶液包括溶解之銀離子,水,視需要之一種或多種溶解之合金金屬如錫或銅,足以賦予鍍覆浴導電性之用量的酸電解質如甲烷磺酸,以及改良鍍覆的均勻性和金屬沉積物的品質之專有的添加劑。該些添加劑尤其包含錯合劑,界面活性劑,及晶粒細化劑。
美國專利第6,998,036號揭露一種含有某種硫化物或經硫醇取代之醚化合物之酸性錫-銀合金電鍍浴。已發現,唯一示
例之化合物3,6-二硫雜辛二醇-1,8在延長儲存或長期使用時會聚合,導致從電鍍浴沉澱出銀。
美國專利第7,628,903號揭露一種含有某些硫化物化合物之習知銀及銀合金電鍍浴。此專利聲稱這些電鍍浴具有良好安定性。然而,已發現在延長儲存或長期使用時,該些硫化物化合物在錫-銀合金電鍍浴中聚合或分解,導致從電鍍浴沉澱出銀。
對在儲存或長期使用時具有足夠的安定性且提供符合各種應用之焊料性能準則之錫-銀合金沉積物之銀及銀-合金電鍍浴,特別是錫-銀合金電鍍浴依然有需求。
本發明係提供一種電鍍組成物,包括:浴可溶之銀離子來源;水;酸電解質;及下式之硫化物化合物:Y1-(CR1R2)m-S-(CR3R4)x-S-(CR5R6)n-Y2式中Y1及Y2獨立選自CO2H,SO3H,PO3H2,CONR7R8及OH;各R1,R2,R5及R6獨立選自H,(C1-C6)烷基,CO2H,及經羥基取代之(C1-C6)烷基;各R3及R4獨立選自H及(C1-C6)烷基;m=1至6;n=1至6;R7及R8獨立選自H及(C1-C3)烷基;及x=1至6;惟當Y1=OH時,m=3;限制條件為當Y2=OH時,n=3;以及限制條件為當R1,R2,R5及R6之任一者為經羥基取代之(C1-C6)烷基時,此羥基係鍵結於對硫原子而言為至少γ之碳原子。該種電鍍組成物可進一步包含一種或多種合金金屬及一種或多種助劑。
本發明亦提供一種在基板上沉積銀或銀-合金層之方法,包括使基板與包括下述者之電鍍組成物接觸:浴可溶之銀離子來源;水;酸電解質;及下式之硫化物化合物:
Y1-(CR1R2)m-S-(CR3R4)x-S-(CR5R6)n-Y2(式中Y1及Y2獨立選自CO2H,SO3H,PO3H2,CONR7R8及OH;各R1,R2,R5及R6獨立選自H,(C1-C6)烷基,CO2H,及經羥基取代之(C1-C6)烷基;各R3及R4獨立選自H及(C1-C6)烷基;m=1至6;n=1至6;R7及R8獨立選自H及(C1-C3)烷基;及x=1至6;限制條件為當Y1=OH時,m=3;限制條件為當Y2=OH時,n=3;以及限制條件為當R1,R2,R5及R6之任一者為經羥基取代之(C1-C6)烷基時,此羥基係鍵結於對硫原子而言為至少γ之碳原子);以及施加一段時間的電位以在基板上沉積含錫-銀之層。
本說明書全文中所使用之下列縮寫應具有下列意義,除非文中另有清楚地說明:ASD=A/dm2=每平方分米之安培;℃=攝氏溫度;g=公克;mg=毫克;L=公升;Å=埃;μm=微米(micron)=微米(micrometer);mm=毫米;min=分鐘;DI=去離子;及mL=毫升。所有的用量皆為重量百分比("wt%")且所有的比率皆為莫耳比率,除非另有說明。所有的數值範圍皆包含邊值且可以任何順序組合,除非顯然該些數值範圍侷限於加總至100%。
本說明書全文中所使用之用語,"鍍覆"係指金屬電鍍。本說明書全文中交替地使用"沉積"及"鍍覆"。"鹵化物"係指氯化物,溴化物,碘化物及氟化物。冠詞"一(a)"和"一(an)"係指單數及複數。"烷基"係指直鏈,支鏈及環狀烷基。"芳基"係指芳香族碳環及芳香族雜環。
令人意想不到地發現在銀或銀-合金電鍍浴中使用下式之硫化物化合物,可改良電鍍浴的安定性。
Y1-(CR1R2)m-S-(CR3R4)x-S-(CR5R6)n-Y2式中Y1及Y2獨立選自CO2H,SO3H,PO3H2,CONR7R8及OH;各R1,R2,R5及R6獨立選自H,(C1-C6)烷基,CO2H,及經羥基取代之(C1-C6)烷基;各R3及R4獨立選自H及(C1-C6)烷基;m=1至6;n=1至6;R7及R8獨立選自H及(C1-C3)烷基;及x=1至6;限制條件為當Y1=OH時,m=3;限制條件為當Y2=OH時,n=3;以及限制條件為當R1,R2,R5及R6之任一者為經羥基取代之(C1-C6)烷基時,此羥基係鍵結於對硫原子而言為至少γ之碳原子。該種硫化物化合物係作為銀電鍍浴中之錯合劑。
其上可電鍍銀或含銀合金之任何基板皆可使用於本發明。該種基板包含,但不限於,電子裝置如印刷電路板,導線框架,互連及半導體基板。本文所用"半導體基板"一詞係包含具有一層或多層半導體層之任何基板或者包含一種或多種半導體裝置之主動或可操作部份之結構的基板。"半導體基板"一詞係指包括半導體材料之任何構造,包含但不限於整塊半導體材料如半導體晶圓(單獨或包括其上之其他材料之組裝件),以及半導體材料層(單獨或包括其他材料之組裝件)。半導體裝置係指其上已經或正在批次製造至少一個微電子裝置之半導體基板。本文所用"晶圓"一詞係包含"基板","半導體基板","半導體裝置",及各種水平之互連之各種封裝,包含單晶片晶圓,多晶片晶圓,各種等級之封裝,或需要焊料連接之其他組裝件。特別適合之基板為圖案化晶圓,如圖案化矽晶圓及圖案化鎵-砷化物晶圓。該種晶圓可為任
何適合的尺寸。較佳之晶圓直徑為200mm至300mm,雖然具有較小及較大直徑之晶圓亦可依據本發明予以電鍍。
任何浴可溶之銀離子來源皆可使用於本案之電鍍浴。本文所用金屬離子之"浴可溶"來源一詞係指可溶於本酸電鍍浴之金屬離子之來源。適合之銀化合物的實例包含,但不限於,氧化銀,硝酸銀,烷磺酸銀,芳基磺酸銀,碘化銀,氯化銀,及硫酸銀。較佳為氧化銀及甲烷磺酸銀。可使用浴可溶銀化合物的混合物。
本案之電鍍浴可使用廣範圍用量之浴可溶銀化合物,視沉積物中所要之銀用量而定。選擇該銀化合物用量係在技術領域中具有通常知識者的能力之內。電鍍浴中之銀濃度的適合範圍為0.05至50g/L之銀。沉積銀之電鍍浴可含有20至50g/L之銀。銀-合金電鍍浴可含有變化用量之銀,如0.1至25g/L,視欲沉積之特定銀-合金而定。例如,當希望具有0.1至10wt%銀之銀合金,如錫-銀時,本案之電鍍浴中之示例銀濃度可為0.05至10g/L,較佳為0.1至10g/L,更佳為0.1至8g/L,又更佳為0.1至5g/L。對高速製程而言,銀的適合濃度為0.5至8g/L。
浴可溶而且不會負面地影響電解質組成物之酸電解質皆可使用於本發明。適合之酸電解質包含,但不限於:烷磺酸,如甲烷磺酸,乙烷磺酸及丙烷磺酸;芳基磺酸如苯基磺酸,甲苯磺酸,酚磺酸,及甲酚磺酸;硫酸;磺胺酸;以及無機酸如氫氯酸,氫溴酸及氟硼酸。烷磺酸及芳基磺酸為較佳之酸電解質,更佳為烷磺酸。特佳為甲烷磺酸。酸電解質的混合物特別有用,如,但不限於,烷磺酸與硫酸之混合物。因此,超過一種酸電解質可
有利地使用於本發明。可使用於本發明之酸性電解質通常可自市面購得,且無需進一步純化即可使用。或者,此等酸電解質可藉由文獻中已知之方法製備之。通常,本案之電鍍浴中之酸電解質的用量為10至400g/L,較佳為100至400g/L,更佳為150至350g/L。
本發明之銀或銀-合金電鍍浴含有一種或多種下式之硫化物化合物:Y1-(CR1R2)m-S-(CR3R4)x-S-(CR5R6)n-Y2,式中Y1及Y2獨立選自CO2H,SO3H,PO3H2,CONR7R8及OH;各R1,R2,R5及R6獨立選自H,(C1-C6)烷基,CO2H,及經羥基取代之(C1-C6)烷基;各R3及R4獨立選自H及(C1-C6)烷基;m=1至6;n=1至6;R7及R8獨立選自H及(C1-C3)烷基;及x=1至6;限制條件為當Y1=OH時,m=3;限制條件為當Y2=OH時,n=3;以及限制條件為當R1,R2,R5及R6之任一者為經羥基取代之(C1-C6)烷基時,此羥基係鍵結於對硫原子而言為至少γ之碳原子。短語"此羥基係鍵結於對硫原子而言為至少γ之碳原子"係指離硫原子3個碳或更多碳之羥基。亦即,羥基可為離硫原子3,4,5,6,7,8,9,或10個碳,較佳為離硫原子3,4,5,6,7,或8個碳,更佳為離硫原子3,4,5,或6個碳,最佳為離硫原子3個碳。各R1,R2,R5及R6較佳獨立選自H,(C1-C4)烷基,CO2H,及經羥基取代之(C1-C4)烷基,更佳選自H,(C1-C4)烷基,及經羥基取代之(C1-C2)烷基,又更佳選自H,(C1-C2)烷基,及經羥基取代之(C1-C2)烷基,再又更佳選自H及經羥基取代之(C1-C2)烷基。R7及R8較佳獨立選自H,甲基及乙基,更佳為H及甲基。較佳係R7=R8,更佳係R7=R8=H。Y1及Y2較佳各自選自CO2H,SO3H,PO3H2,及OH,更佳選自CO2H,SO3H及PO3H2,又更佳選自CO2H及SO3H。或者,Y1
及Y2獨立選自CO2H,SO3H,及OH。較佳係m=1至4,更佳為1-3。較佳係n=1至4,更佳為n=1至3。較佳係x=1至4,更佳為1-3,又更佳為1-2。Y1與Y2較佳係相同,亦即,較佳Y1=Y2。又更佳係Y1及Y2獨立選自CO2H,SO3H,及OH;各R1,R2,R5及R6獨立選自H,(C1-C3)烷基,及經羥基取代之(C1-C3)烷基;各R3及R4獨立選自H及(C1-C3)烷基;m=1至4;n=1至4;及x=1至4。示例之經羥基取代之(C1-C6)烷基包含:2-羥基-1-乙基;2-羥基-1-丙基;3-羥基-2-丁基;2-羥基-2-丙基;2-羥基-2-甲基-2-丙基;2-羥基-1-丁基;2-羥基-2-甲基-2-丁基;1-羥基-2-丁基;2-羥基-2-甲基-1-丙基;3-羥基-2-丁基;及2-羥基甲基-2-丁基。
示例之硫化物化合物包含,不限於:雙-(3-羥基丙基)-1,2-二硫基乙烷;2,2'-((乙烷-1,2-二基雙(硫烷二基))雙亞甲基)雙(2-(羥基甲基)丙烷-1,3-二醇);3,3'-(亞甲基雙(硫烷二基))二丙醇;2,2'-(亞甲基雙(硫烷二基))二琥珀酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙烷磺酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二丙基磺酸酯;3,3'-(乙烷-1,2-二基雙(硫烷二基))二丙酸;2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙酸;2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙烷磺酸;3,3'-(乙烷-1,2-二基雙(硫烷二基))雙(丙烷-1-磺酸);((乙烷-1,2-二基雙(硫烷二基))雙(丙烷-3,1-二基))二膦酸;((乙烷-1,2-二基雙(硫烷二基))雙(乙烷-2,1-二基))二膦酸;及((亞甲基雙(硫烷二基)雙(乙烷-2,1-二基))二膦酸。較佳之硫化物化合物為:雙-(3-羥基丙基)-1,2-二硫基乙烷;2,2'-((乙烷-1,2-二基雙(硫烷二基))雙亞甲基)雙(2-(羥基甲基)丙烷-1,3-二醇);3,3'-(亞甲基雙(硫烷二基))二丙醇;2,2'-(亞甲基雙(硫
烷二基))二琥珀酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙烷磺酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二丙基磺酸酯;3,3'-(乙烷-1,2-二基雙(硫烷二基))二丙酸;2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙酸;2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙烷磺酸;及3,3'-(乙烷-1,2-二基雙(硫烷二基))雙(丙烷-1-磺酸)。更佳之硫化物化合物為2,2'-((乙烷-1,2-二基雙(硫烷二基))雙亞甲基)雙(2-(羥基甲基)丙烷-1,3-二醇);2,2'-(亞甲基雙(硫烷二基))二琥珀酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙烷磺酸;2,2'-(丙烷-1,3-二基雙(硫烷二基))二丙基磺酸酯;3,3'-(乙烷-1,2-二基雙(硫烷二基))二丙酸;2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙酸;2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙烷磺酸;及3,3'-(乙烷-1,2-二基雙(硫烷二基))雙(丙烷-1-磺酸)。
一般而言,以電鍍浴中之銀離子的莫耳數計之,一種或多種硫化物化合物係以1至10當量之用量存在於電鍍浴中。硫化物化合物較佳以1至8當量,更佳為1.5至8當量,又更佳為2至6當量之用量存在之。通常,硫化物化合物可以各式各樣的濃度存在於本案之電鍍浴中。例如,在錫-銀合金電鍍浴中,硫化物化合物通常係以0.01至25g/L,較佳為0.5至25g/L,更佳為0.5至20g/L,又更佳為0.5至15g/L,再又更佳為0.5至10g/L之濃度使用之。
硫化物化合物通常可自市面購得或者可藉由文獻中已知之方法製備之。該些化合物可無需進一步純化即可使用,或在使用前可進一步純化之。本案之硫化物化合物為浴可溶者。較
佳之硫化物化合物在17%甲烷磺酸/DI水溶液中具有≧5mg/L,較佳為>5mg/L,更佳為≧10mg/L,又更佳為≧20mg/L,再又更佳為≧30mg/L之溶解度。對於本案之電鍍浴中之硫化物化合物的最大溶解度沒有要求,因為該最大溶解度並非關鍵。一般而言,在17%甲烷磺酸/DI水溶液中,硫化物化合物具有≧5至250mg/L或更大之溶解度。
本案之電鍍浴可視需要地包含一種或多種合金金屬。可被電鍍之與銀形成合金之任何金屬皆可適合地使用之。較佳之合金金屬包含鎵,錫,銅,及其混合物,更佳為錫,銅,及其混合物。該種合金金屬係以浴可溶形式,如相對應之氧化物,鹵化物,硝酸鹽,硫酸鹽,羧酸鹽,烷基磺酸鹽或芳基磺酸鹽,較佳為羧酸鹽,烷基磺酸鹽或芳基磺酸鹽添加至電鍍浴中。該些合金金屬的用量係視欲沉積之合金定之。該些合金金屬及其用量的選擇係在技術領域中具有通常知識者的知識之內。
本案之電鍍浴較佳含有錫離子作為合金金屬。任何浴可溶之二價錫鹽皆可適用於本發明。該種錫化合物的實例包含,但不限於,氧化錫及鹽類如錫鹵化物,硫酸錫,烷磺酸錫如甲烷磺酸錫,芳基磺酸錫如苯基磺酸錫,酚磺酸錫,及甲苯磺酸錫,烷醇磺酸錫等。當使用錫鹵化物時,鹵化物較佳為氯化物。錫化合物較佳為氧化錫,硫酸錫,氯化錫,烷磺酸錫或芳基磺酸錫。錫鹽更佳為甲烷磺酸,乙烷磺酸,丙烷磺酸,2-羥基乙烷-1-磺酸,2-羥基丙烷-1-磺酸,或1-羥基丙烷-2-磺酸之亞錫鹽,又更佳為甲烷磺酸錫。可使用錫鹽之混合物。可使用於本發明之錫化合物通常可購自市面之各式各樣的來源,且無需進一步純化即可
使用。或者,可使用於本發明之錫化合物可藉由文獻中已知之方法製備之。
使用於本案之電鍍浴之浴可溶錫離子來源的用量可在廣範圍上變化之。浴可溶錫離子來源之適合用量為5至100g/L,較佳為5至85g/L,更佳為10至85g/L。錫離子來源之適合用量可隨應用而變。例如,5至25g/L之錫離子來源可使用於低速製程,而30至85g/L使用於高速製程。
除了上述成分外,本案之電鍍浴可視需要地包含一種或多種"助劑"。本文所用之助劑係指除了主要成分(銀化合物,酸性電解質,水,視需要之金屬合金)外之可添加至組成物,且其有助於主要成分的有效性之添加劑或化合物。適合之助劑的實例包含,但不限於,亮光劑,抗氧化劑,界面活性劑,晶粒細化劑,導電性酸和其鹽類,及其混合物。助劑清單並未全部列出,而改良銀沉積之有效性之任何化合物及元素皆可使用於實施本發明。該些助劑可以習知用量使用之。
當希望光澤表面時,可使用亮光劑。適合之亮光劑包含,但不限於,醛,酮,羧酸,羧酸衍生物,胺或其混合物。適合之亮光劑的特定實例可在美國專利第4,582,576及4,246,077號中找到。該種亮光劑的用量可為鍍覆浴之50mg/L至5g/L,通常為100mg/L至250mg/L。鐵,鈷,鎳,鋅,鎵,砷,硒,鈀,鎘,銦,銻,碲,鉈,鉛及鉍之化合物皆適合。聚乙二醇及其衍生物,如聚乙二醇醚,至其為浴可溶之程度,亦為適合之亮光劑。聚乙二醇及其衍生物可作為唯一亮光劑,或其可與上述揭露之其他亮光劑一起使用。
當存在錫離子時,可添加抗氧化劑至本案之組成物,以使錫保持在可溶之二價狀態。適合之抗氧化劑包含,但不限於,氫醌及羥基化之芳香族化合物,如雷瑣酚,兒茶酚等,包含該種芳香族化合物之磺酸衍生物。該種抗氧化劑揭露於美國專利第4,871,429號。其他適合之抗氧化劑或還原劑包含,但不限於,釩化合物,如乙醯基丙酮氧釩,三乙醯基丙酮酸釩,鹵化釩,氧鹵化釩,烷氧化釩及烷氧化氧釩。該種還原劑的用量對技術領域中具有通常知識者而言係眾所周知者,但通常為0.1g/L至5g/L。
一種或多種界面活性劑可視需要地使用於本案之電鍍浴中。該種界面活性劑包含,但不限於,非離子性界面活性劑,陰離子性界面活性劑,兩性界面活性劑及陽離子性界面活性劑。視需要之界面活性劑較佳選自一種或多種非離子性界面活性劑,陰離子性界面活性劑,及兩性界面活性劑。適合之非離子性界面活性劑包含那些其中2至300莫耳環氧乙烷(EO)及/或環氧丙烷(PO)與下述任一者縮合者:(C1-C20)烷醇,酚,萘酚,雙酚,(C1-C25)烷基酚,芳基烷基酚,(C1-C25)烷基萘酚,(C1-C25)烷氧基化磷酸(鹽),山梨醇酯,苯乙烯化酚,聚伸烷二醇,(C1-C22)脂肪族胺,(C1-C22)脂肪族醯胺;或(C1-C25)烷氧基化磷酸(鹽)等。該種界面活性劑通常可購自市面之各式各樣的來源。
可使用於本案之電鍍浴之另一較佳之界面活性劑為烷氧基化胺氧化物界面活性劑。雖然已知有各式各樣的胺氧化物界面活性劑,但較佳使用低發泡之烷氧基化胺氧化物界面活性劑。較佳之烷氧基化胺氧化物界面活性劑具有使用備有#2轉軸之Brookfield LVT黏度計所測得之小於500厘泊(cps)之黏度。此黏度
通常係在常溫(大約20℃)測定之。較佳之烷氧基化胺氧化物具有下式:
式中,Ra係選自(C6-C22)烷基及經取代之(C7-C22)芳基;Rb為烷氧基化單元;m為0至7且表示Rb的莫耳數;n為0或1;及Rc和Rd各為至少一個烷氧基化單元,且Rc與Rd所示之烷氧基化單元的總數為3至30。烷氧基化單元係指添加至胺之個別環氧烷單元。適合之環氧烷單元包含乙烯氧基,丙烯氧基,丁烯氧基,及其混合物,包含異構物。Ra較佳係選自(C6-C22)烷基。Rb可選自各種環氧烷單元,如氧化苯乙烯,乙烯氧基,丙烯氧基,丁烯氧基及其混合物。Rb之烷氧基化單元較佳係選自乙烯氧基,丙烯氧基,丁烯氧基及其混合物。Rc和Rd之較佳烷氧基化單元包含乙烯氧基,丙烯氧基,及丁烯氧基單元,包含其混合物。Rc和Rd較佳各選自乙烯氧基,丙烯氧基,及其混合物。Rc和Rd更佳各為乙烯氧基單元。較佳之胺氧化物界面活性劑包含在Rc和Rd中存在5至20莫耳烷氧基化單元。Rc和Rd更佳包含5至15莫耳烷氧基化單元。特別適合之胺氧化物界面活性劑為那些其中Rc和Rd各由選自乙烯氧基單元、丙烯氧基及其混合物之3.5至10莫耳烷氧基化單元所組成者。較佳係m=0。較佳係n=1。更佳為其中m=0且n=1之胺氧化物,更佳係Ra為(C6-C22)烷基。又更佳之胺氧化物為那些其中m=0,n=1,Ra為(C6-C22)烷基,且Rc和Rd各為伸乙氧基單元者。
烷氧基化胺氧化物界面活性劑通常可自市面購得或
由已知程序,如那些見述於美國專利第5,972,875號者製備之。較佳之胺氧化物界面活性劑為那些Air Products出品,以Tomamine品牌販售者,如那些具有AO-14-2,AO-728,AO-405及AO-455稱號者。胺氧化物界面活性劑在本案之電鍍中的用量為0.1至50g/L,較佳為0.1至25g/L,更佳為0.5至25g/L,又更佳為1至20g/L,再又更佳為5至20g/L。
晶粒細化劑可視需要地使用於本案之電鍍浴中。當使用錫-銀合金電鍍浴時,較佳使用一種或多種晶粒細化劑。任何適合之晶粒細化劑皆可使用於本發明。該種化合物對沉積物提供良好晶粒結構同時對由組成物所沉積之互連凸塊(焊料凸塊)提供均勻之蘑菇形態。晶粒細化劑較佳為黄酮化合物。該種黄酮化合物包含,但不限於,白楊黃素,漆黃素,楊梅黄酮,芸香素,以及五羥基黄酮如桑色素及槲皮苷。適合之黄酮化合物係那些揭露於美國專利第7,968,444號者。黄酮化合物可以1至200mg/L,較佳為10至100mg/L,更佳為25至85mg/L之用量存在。
本案之組成物可視需要地包含一種或多種晶粒細化劑/安定劑化合物以進一步改良電鍍操作窗(window)。較佳在本發明組成物中存在一種或多種晶粒細化劑/安定劑化合物。該種晶粒細化劑/安定劑化合物包含,但不限於,羥基化γ-吡喃酮如麥芽醇,乙基麥芽醇,麴酸,罌粟酸,及可孟酸;羥基化苯醌如二氯氫醌及二羥基苯醌;羥基化萘酚如變色酸;蒽醌;羥基化吡啶;環戊二酮;羥基呋喃酮;羥基-吡咯烷酮;及環己二酮。該種化合物可以2至10,000mg/L,較佳為50至2000mg/L之用量包含在組成物中。
導電性酸及其鹽類亦可使用於本案之組成物中,包含,但不限於,硼酸,羧酸,羥基酸,及這些酸的鹽類至其為浴可溶之程度。較佳為甲酸,乙酸,草酸,檸檬酸,蘋果酸,酒石酸,葡萄糖酸,葡萄糖二酸,葡萄糖醛酸,及這些酸的鹽類。該種導電性酸及鹽類係以習知用量使用之。
本發明之電鍍浴係藉由組合下述者而製備之:浴可溶之銀離子來源;酸電解質;上述之硫化物化合物,及任何下述之視需要的成分:一種或多種浴可溶之合金金屬來源,亮光劑,抗氧化劑,界面活性劑,晶粒細化劑,導電性酸和其鹽類,及其混合物,組成物之其餘成分為水。該些成分可以任何順序組合之。所使用之水較佳為DI水。各上述成分的用量可調整,且視特定應用予以適當選擇。一旦組成物製備好,即可藉由如過濾移除不想要的材料,然後通常添加額外的水以調整組成物的最終體積。可藉由任何已知的手段,如攪拌,抽泵,或循環攪動此組成物而增加鍍覆速度。本案之銀或銀合金電鍍組成物為酸性,亦即,其具有小於7之pH。本案之電鍍組成物通常具有0至小於7,較佳為0至≦5,更佳為0至≦2,又更佳為0至≦1之pH。
本案之電鍍浴較佳實質上不含氰離子。"實質上不含"一詞係指組成物含有小於1wt%之該成分,較佳為有小於0.5wt%之該成分。
本案之電鍍組成物適合於在基板上沉積含銀之層。"含銀之層"一詞係指銀層及銀合金層兩者。在該種銀合金層中,銀及一種或多種合金金屬可以各種用量存在。該種銀合金層包含,不限於,錫-銀,錫-銀-銅,錫-銀-銅-銻,錫-銀-銅-錳,錫-銀-鉍,
錫-銀-銦,錫-銀-鋅-銅,及錫-銀-銦-鉍。本案之電鍍組成物較佳沉積錫-銀或錫-銀-銅,更佳為錫-銀之沉積物。以合金之重量計之,自本案之電鍍浴所沉積之錫-銀合金含有0.01至99.99wt%量之錫,及99.99至0.01wt%量之銀,此係藉由原子吸收光譜儀(AAS),X射線螢光光譜儀(XRF),感應耦合電漿(ICP)或差示掃描量熱儀(DSC)測得者。使用本發明所沉積之錫-銀合金較佳含有75至99.99wt%錫及0.01至10wt%銀以及任何其他合金金屬。錫-銀合金沉積物更佳含有95至99.99wt%錫及0.1至5wt%銀以及任何其他合金金屬。錫-銀合金為較佳之沉積物,且較佳含有90至99.99wt%錫及10至0.1wt%銀。錫-銀合金沉積物更佳含有95至99.99wt%錫及5至0.1wt%銀。對許多應用而言,可使用銀合金之共熔組成物。依據本發明所沉積之銀合金實質上不含鉛,亦即,其含有≦1wt%,更佳為≦0.5wt%,又更佳為≦0.2wt%之鉛,再又更佳為不含鉛。
本發明之電解質組成物有用於期望銀或銀合金層之各種鍍覆方法。該鍍覆方法包含,但不限於,平行或垂直晶圓鍍覆,筒式鍍覆,掛式鍍覆(rack plating),高速鍍覆如卷至卷及噴射鍍覆,以及無掛式鍍覆。銀或銀合金層可藉由使基板與上述電解質組成物接觸再使電流通過電解質以使含銀之層沉積在基板上之步驟沉積在基板上。可被鍍覆之基板包含,但不限於,銅,銅合金,鎳,鎳合金,含鎳-鐵之材料,電子元件,塑膠,及半導體晶圓如矽或鎵-砷化物晶圓。可被鍍覆之塑膠包含,不限於,塑膠層合物,如印刷電路板,特別是銅包層印刷電路板。此電解質組成物可使用於電鍍電子元件,如導線框架,半導體晶圓,半導體封
裝件,元件,連接器,接點,晶片電容器,晶片電阻,印刷電路板,及晶圓互連凸塊鍍覆應用。基板可以技術領域中已知之任何方式與電解質組成物接觸。基板通常係放置在含有電解質組成物之槽中。
使用特定之電流密度使銀或銀合金沉積,視特定之鍍覆方法而定。一般而言,電流密度為1A/dm2,如較佳為1至200A/dm2,更佳為2至30A/dm2,又更佳為5至20A/dm2,再又更佳為8至20A/dm2。
銀或銀合金可在15℃或更高,較佳為15至66℃,更佳為20至55℃之溫度沉積。通常,對特定溫度及電流密度而言,時間愈長,基板鍍覆之沉積物愈厚,而時間愈短,沉積物愈薄。因此,基板留在鍍覆組成物中之時間長度可使用於控制所得含銀之沉積物的厚度。通常,金屬沉積速率可高達15μm/min,或更高。一般而言,沉積速率可為1至10μm/min,更佳為3至8μm/min。
雖然本案之電解質組成物可使用於如上述之各式各樣的應用,一種示例之應用係用於晶圓-水平-封裝之互連凸塊(焊料凸塊)形成。此方法涉及提供具有複數個互連凸塊墊之半導體晶片(晶圓晶片),在互連凸塊墊上形成種子層,藉由使半導體晶片與本案之電解質組成物接觸且使電流通過電解質組成物以使含銀之層之互連凸塊層沉積在基板上而在互連凸塊片上沉積含銀之互連凸塊層(較佳為銀-合金層如錫-銀合金),然後使互連凸塊層迴銲以形成焊料凸塊。
通常,裝置包含其上形成著複數個導電性互連凸塊
墊之半導體基板。半導體基板可為單結晶矽晶圓,矽-鍺基板,鎵-砷化物基板,藍寶石上矽(SOS)基板,或絕緣體上矽(SOI)基板。導電性互連凸塊片可為通常藉由物理汽相沉積(PVD)如濺鍍所形成之一層或多層金屬,複合金屬或金屬合金。典型之導電性互連凸塊片材料包含,不限於,鋁,銅,氮化鈦,及其合金。
藉由蝕刻製程,通常為乾式蝕刻,在互連凸塊墊上形成鈍化層及在其中形成延伸至互連凸塊墊之開口。鈍化層通常為絕緣材料,例如,氮化矽,氧氮化矽,或氧化矽,如磷矽酸鹽(PSG)。該些材料可藉由化學汽相沉積(CVD)製程,如電漿強化CVD(PECVD)予以沉積。
在裝置上沉積通常係由複數層金屬或金屬合金層所形成之凸塊下金屬化(UBM)結構。UBM係作為欲形成之互連凸塊的黏合層及電氣接點基底(種子層)。形成UBM結構之層可藉由PVD,如濺鍍或蒸鍍,或者CVD製程沉積之。UBM結構可為但不限於,例如,依序包含底鉻層,銅層,及上錫層之複合結構。
對裝置塗敷光阻層,接著標準微影曝光及顯影技術以形成其中具有開口或通孔(鍍覆通孔)之經圖案化之光阻層。鍍覆遮罩的尺寸(鍍覆遮罩的厚度及圖案中之開口的尺寸)係定義沉積在I/O片及UBM上之含銀層的尺寸及位置。該種沉積物的直徑通常為5至300μm,較佳為10至150μm。該種沉積物的高度通常為10至150μm,較佳為15至150μm,更佳為20至80μm。適合之光阻材料可自市面購得(如Dow Electronic Materials,Marlborough,Massachusetts,USA出品),且為技術領域眾所周知者。
互連凸塊材料係藉由使用上述之電鍍組成物以電鍍
製程沉積在裝置上。互連凸塊材料包含,例如,銀及任何適合之銀合金如錫-銀,錫-銀-銅等。該些合金可具有如上述者之組成。可希望在其共熔濃度使用該些組成。凸塊材料係電鍍在由鍍覆通孔所界定之區域中。為了此目的,通常使用具備直流電(DC)或脈衝鍍覆技術之水平或垂直晶圓鍍覆系統,例如,噴鍍系統。在鍍覆製程中,互連凸塊材料完全地填充延伸其上之通孔及在鍍覆遮罩之頂表面之一部份上,導致蘑菇形狀之金屬沉積物。此確保沉積足夠體積之互連凸塊材料以在迴銲後達成所要之球尺寸。在通孔鍍覆製程中,光阻厚度足夠厚使得適當體積之互連凸塊材料含在鍍覆遮罩通孔內。在鍍覆互連凸塊材料之前,可在鍍覆通孔中電沉積銅層或鎳層。該層可作為迴銲時對互連凸塊之可潤濕基層。
互連凸塊材料沉積後,使用適當的溶劑或其他移除劑剝離鍍覆遮罩。該些移除劑為技藝中眾所周知者。然後使用已知技術選擇性地蝕刻UBM結構,自互連凸塊周圍及之間之場區域移除所有金屬。
然後視需要地使晶圓熔化且在迴銲烘箱中加熱至互連凸塊材料熔化並流動成截頭之大致上球形之形狀的溫度。加熱技術係技術領域中眾所周知者,包含,例如,紅外線,傳導,及對流技術,及其組合。此回流之互連凸塊通常與UBM結構之邊緣共同延伸。此加熱處理步驟可在惰性氣氛或空氣中進行之,而特定之製程溫度及時間係視互連凸塊材料之特定組成而定。
或者,本案之電鍍組成物可使用於在焊料沉積物上沉積銀或銀合金覆蓋層。較佳使用銀合金於覆蓋層。例如,錫-銀合金可沉積在銅柱體之頂部上,如使用於製造覆晶互連者。當
使用作為銅柱體上之覆蓋層時,該經覆蓋之銅柱體的總高度可為20至50μm,且可具有30至45μm之直徑,雖然其他尺寸亦適合。在又一選擇方案中,該種覆蓋層焊料沉積物可含有複數層之覆蓋層。可與本案之含銀層一起使用之其他適合之覆蓋層包含:純錫及錫-合金如錫-鉍及錫-銅。當使用複數層之覆蓋層時,含銀層通常係在最外層。
3,3'-(乙烷-1,2-二基雙(硫烷二基))二丙烷醯胺(化合物1):將四硼酸鈉(1.20g,5.95mmol)溶解在DI水(150mL)中。添加1,2-乙烷二硫醇(5.00mL,59.4mmol),接著丙烯醯胺(9.31g,130mmol),於室溫攪拌兩小時,得到白色漿料。濾除固體,以水沖洗,在真空下予以乾燥,得到13.1g(93.2%)呈白色固體之化合物1。1H NMR(500MHz,d6-DMSO)δ 7.33(s,2H),6.82(s,2H),3.37(s,4H),2.69(t,J=7.2Hz 4H),2.32(t,J=7.3Hz,4H)。13C NMR(126MHz,d6-DMSO)δ 172.68,35.69,31.35,26.92。
3,3'-(乙烷-1,2-二基雙(硫烷二基))二丙酸(化合物2):基本上重複實施例1的程序,但以丙烯酸甲酯取代丙烯醯胺以形成二酯化合物3,3'-(乙烷-1,2-二基雙(硫烷二基))二丙酸二甲酯。加熱此二酯(5.00g,18.8mmol)以在2N HCl(50mL)中迴流兩小時,然後冷卻至室溫過夜,得到白色沉澱物。濾除固體,以水沖洗,在真空下予以乾燥,得到4.26g(95.2%)呈白色固體之化合物2。1H NMR(500MHz,d6-DMSO)δ 12.10(s,2H),2.61(t,J=7.1Hz,4H),2.60(s,4H),2.40(t,J=7.1Hz,4H)。13C NMR(126MHz,
d6-DMSO)δ 172.98,31.70,31.47,26.44。
2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙酸(化合物3):將1,2-乙烷二硫醇(5.00mL,59.4mmol)溶解在CH2Cl2(100mL)中,而且添加Et3N(15.0g,149mmol)。然後使此混合物冷卻至0℃,而且緩慢地逐滴添加在CH2Cl2(25mL)中之溴甲基乙酸鹽(19.1g,125mmol)之溶液。添加完成後,使反應混合物溫熱至常溫再攪拌兩小時。以0.5M HCl(100mL),NaHCO3飽和水溶液,食鹽水沖洗有機相,以Na2SO4乾燥,然後濃縮,得到12.9g(90.8%)呈澄清油之二酯化合物,2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙酸二甲酯。1H NMR(500MHz,CDCl3)δ 3.74(s,6H),3.28(s,4H),2.89(s,4H)。13C NMR(126MHz,CDCl3)δ 170.53,52.31,33.15,31.87。
加熱2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙酸二甲酯(7.00g,29.4mmol)以在2N HCl(50mL)中迴流兩小時。使此混合物冷卻至室溫得到澄清溶液,使其真空中濃縮至乾燥,得到5.98g(96.8%)呈白色固體之化合物3。1H NMR(400MHz,D2O)δ 3.47(s,4H),2.95(s,4H)。13C NMR(101MHz,D2O)δ 174.61,33.28,31.39。
2,2'-(乙烷-1,2-二基雙(硫烷二基))二乙烷磺酸(化合物4):於0℃對在EtOH(350mL)中之2-溴乙基磺酸鈉鹽(25.6g,125mmol)及甲醇鈉(8.03g,149mmol)之溶液逐滴添加在EtOH(25mL)中之1,2-乙烷二硫醇(5.00mL,59.4mmol)溶液。使反應混合物溫熱至室溫,然後加熱至迴流48小時。其次,使此混合物冷卻至室溫,然後以2N HCl予以酸化至pH 1至2。將所得之懸浮液加熱至
75℃,再以小部份緩慢地添加水直至得到澄清溶液。然後使反應混合物冷卻至室溫,然後至5℃。濾除所得之白色沉澱物,以冷EtOH予以沖洗再乾燥之,得到11.9g(64.6%)呈白色粉末之化合物4。1H NMR(500MHz,D2O)δ 3.27(t,J=9.3,6.4Hz,4H),3.06-2.99(m,4H),2.98(s,4H)。13C NMR(126MHz,D2O)δ 51.11,31.09,25.58。
3,3'-(乙烷-1,2-二基雙(硫烷二基))雙(丙烷-1-磺酸)(化合物5):於周圍溫度對在EtOH(300mL)中之3-溴丙烷磺酸鈉鹽(24.7g,110mmol)及甲醇鈉(7.06g,131mmol)之溶液逐滴添加在乙醇(25mL)中之1,2-乙烷二硫醇(4.4mL,52.3mmol)。使之於室溫攪拌一小時,然後加熱至迴流過夜。冷卻至室溫,再以2N HCl予以酸化至pH 1至2。將所得之懸浮液加熱至75℃,再以小部份緩慢地添加水直至得到澄清溶液。冷卻至室溫,然後至5℃。濾除所得之白色沉澱物,以冷EtOH予以沖洗再乾燥之,得到11.9g(67.4%)白色粉末。1H NMR(400MHz,D2O)δ 3.10(t,J=7.2Hz,4H),2.92(s,4H),2.82(t,J=7.2Hz,4H),2.11(m,4H)。13C NMR(101MHz,D2O)δ 52.26,33.38,32.27,26.80。
3,3'-[1,2-乙烷二基雙(硫基)]雙-1丙醇(化合物6):將在乙腈(50mL)中之3-氯丙醇(56.5g,0.569mol)之溶液緩慢地逐滴添加至在乙腈(100mL)中之1,2-二硫基乙烷(25.0g,0.265mol)及碳酸鈉(70.3g,0.663mol)之溶液。添加完成後,使反應混合物加熱至迴流三小時,然後冷卻至常溫。添加DI水(100mL)以溶解固體,
再以EtOAc(200mL)萃取所得之溶液。以水(100mL)及食鹽水(50mL)沖洗有機相,接著以Na2SO4乾燥。濃縮至乾燥,接著自EtOAc再結晶,得到18.2g呈白色固體之化合物6(33%)。1H NMR(CDCl3)δ 3.76(t,J=6.0Hz,4H),2.76(s,1H),2.68(t,J=7.1Hz,4H),1.97bs,2H),1.86(dd,J=9.6,3.6Hz,4H)。13C NMR(CDCl3)δ 61.50,32.01,32.05,28.79。
3,3'-(亞甲基雙(硫烷二基))二丙醇(化合物7):將3-巰基丙醇(5.20mL,60.5mmol)及粉碎之氫氧化鈉(2.42g,60.5mmol)添加至備有冷凝管及加料漏斗之圓底燒瓶。將此燒瓶放置在冰浴中,而且使燒瓶內容物攪拌。使反應混合物保持在低於20℃時,經由加料漏斗逐滴添加二溴甲烷(2.08mL,30.2mmol)。添加完成後,使反應混合物溫熱至室溫,然後加熱迴流過夜。在此期間,顏色轉成黃色。對此固體殘留物添加不會溶解粗產物之二氯甲烷。添加DI水,且所有內容物成為溶液。在減壓下濃縮反應混合物以移除水及任何二溴甲烷。將粗產物再度溶解於DI水中再經由針筒式過濾器予以過濾,然後濃縮之。使產物在高真空下於80℃靜置以移除任何起始3-巰基丙醇。此未被移除,因此將另外2粒NaOH粉碎,而且攪拌至粗產物中。攪拌入約300μL二溴甲烷。以手攪拌反應小瓶,而且將其放置在於80℃之油浴中過夜以使每種東西皆溶化在一起。濃縮反應混合物且移除二溴甲烷。將產物放置在高真空下以提供6.21克呈淡黃色固體之化合物7。1H NMR(500MHz,D2O)δ 4.14(d,J=19.4Hz,2H),4.01(t,J=6.4Hz,4H),3.07(t,J=7.3Hz,4H),2.24-2.12(m,4H)。13C NMR(126MHz,D2O)
δ 60.92,34.75,31.42,27.79。
2,2'-(亞甲基雙(硫烷二基))二乙酸(化合物8):對圓底燒瓶添加甲醛(10.0mL,124mmol)及硫代乙醇酸(18.9g,206mmol)。攪拌此混合物,而且逐滴添加濃鹽酸(7mL)。使此反應混合物於50℃攪拌一小時,然後於110℃攪拌過夜。使此反應混合物冷卻至室溫,然後於冰箱儲存三天。在此期間,形成白色固體。藉由過濾單離固體,然後自水予以再結晶以得到8.16g(26.22mmol,32.0%)呈白色固體之化合物9。1H NMR(500MHz,d6-DMSO)δ 3.39(s,4H),3.94(s,2H)。13C NMR(126MHz,d6-DMSO)δ 32.65,37.01,173.76。
2,2'-(亞甲基雙(硫烷二基))二琥珀酸(化合物9):對圓底燒瓶添加甲醛(7.95mL,98.3mmol)及巰基琥珀酸(24.6g,163.8mmol)。攪拌此混合物,而且逐滴添加濃鹽酸(7mL)。使此反應混合物於50℃攪拌一小時,然後於110℃攪拌過夜。使此反應混合物冷卻至室溫,然後於冰箱儲存三天。在此期間,形成白色固體。藉由過濾單離固體,然後自水予以再結晶以得到8.16g(26.22mmol,32.0%)呈白色固體之化合物9。1H NMR(500MHz,d6-DMSO)δ 4.01-3.97(m,2H),3.71(ddd,J=12.4,6.2,3.5Hz,2H),2.81-2.71(m,2H),2.64-2.55(m,2H)。13C NMR(126MHz,d6-DMSO)δ 172.73,172.04,40.77,36.12,34.84。
2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙酸(化合物
10):將1,3-丙烷二硫醇(5.00mL,49.9mmol)溶解在CH2Cl2(100mL)中,而且添加三乙胺(17.4mL,125mmol)。使此反應混合物冷卻至0℃,而且逐滴添加在二氯甲烷(50mL)中之溴乙酸甲酯(9.85mL,105mmol)之溶液。添加完成後,使反應混合物溫熱至常溫,而且攪拌兩小時。以0.5M HCl(100mL),NaHCO3飽和水溶液,食鹽水沖洗有機相,以Na2SO4乾燥。使用波紋濾紙過濾有機相,然後在減壓下濃縮之,得到11.3g(44.9mmol,90.0%)呈淡黃色油之2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙酸二甲酯。1HNMR(400MHz,CD2Cl2)δ 3.65(s,6H),3.18(s,4H),2.67(t,J=7.2Hz,4H),1.83(p,J=7.1Hz,2H)。13C NMR(101MHz,CD2Cl2)δ 171.09,52.58,33.73,31.68,28.62。
加熱2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙酸二甲酯(11.3g,44.9mmol),以在2N HCl(50mL)中迴流兩小時。完成時,使此混合物冷卻至室溫。在減壓下濃縮此反應混合物至乾燥,以得到7.29g呈灰白色固體之化合物10(32.5mmol,72.4%)。1H NMR(400MHz,CD2Cl2)δ 11.45(s,2H),3.28(s,4H),2.82-2.69(m,4H),1.92(p,J=7.2Hz,2H)。13C NMR(101MHz,CD2Cl2)δ 177.36,33.93,31.90,28.63。
2,2'-(丙烷-1,3-二基雙(硫烷二基))二乙基磺酸酯(化合物11):於0℃對在乙醇(350mL)中之2-溴乙基磺酸鈉鹽(21.0g,100mmol)及甲醇鈉(5.40g,100mmol)之溶液逐滴添加在EtOH(25.0mL)中之1,3-丙烷二硫醇(5.00mL,50.0mmol)。使此反應混合物溫熱至常溫,然後加熱至迴流48小時。使此反應混合物冷
卻至室溫,然後使用2N HCl予以酸化至pH 1至2。將所得之懸浮液加熱至75℃,而且以小部份緩慢地添加水直至得到澄清淡黃色溶液。使此溶液平衡至室溫,然後冷卻至5℃。濾除所得之白色沉澱物,以冷EtOH予以沖洗再乾燥之。自乙醇再結晶,得到呈白色固體之化合物11(3.99g,24.8%)。1H NMR(400MHz,D2O)δ 3.34-3.13(m,4H),3.07-2.91(m,4H),2.85-2.71(m,4H),2.07-1.90(m,2H)。13C NMR(126MHz,D2O)δ 51.08,29.95,28.16,25.50。
3,3'-(丙烷-1,3-二基雙(硫烷二基))二丙基磺酸酯(化合物12):於室溫對在乙醇(350mL)中之3-溴丙基磺酸鈉鹽(22.4g,100mmol)及甲醇鈉(5.40g,100mmol)之溶液逐滴添加在EtOH(25mL)中之1,3-丙烷二硫醇(5.00mL,50.0mmol)。使此反應混合物加熱至迴流過夜。使此反應混合物冷卻至室溫,然後使用2N HCl予以酸化至pH 1至2。將所得之懸浮液加熱至75℃,而且以小部份緩慢地添加水直至得到澄清淡黃色溶液。使此溶液平衡至室溫,然後冷卻至5℃。濾除所得之白色沉澱物,以冷EtOH予以沖洗再乾燥之。自乙醇再結晶粗產物,以得到10.4g呈白色固體之化合物12(29.69mmol,59.4%)。1H NMR(500MHz,D2O)δ 3.17-3.07(m,4H),2.88-2.73(m,8H),2.18-2.09(m,4H),2.06-1.92(m,2H)。13C NMR(126MHz,D2O)δ 49.88,29.78,28.55,24.26。
2,2'-[1,2-乙烷二基雙(硫基)]雙-乙醇(比較1):將在乙腈(50mL)中之2-氯乙醇(48.1g,0.597mol)之溶液緩慢地逐滴添加至在乙腈(100mL)中之1,2-二硫基乙烷(25.0g,0.265mol)及碳酸鈉
(70.3g,0.663mol)之溶液。添加完成後,使反應混合物加熱至迴流3小時,然後冷卻至常溫。添加DI水(100mL)以溶解固體,再以EtOAc(200mL)萃取所得之溶液。以水(100mL)及食鹽水(50mL)沖洗有機相,接著在Na2SO4上乾燥。濃縮至乾燥,接著自EtOAc再結晶,得到4.60g(9.5%)呈白色固體之比較例1。1H NMR(CDCl3)δ 3.76(t,J=5.9Hz,4 H),2.78(s,4H),2.77(t,J=5.9Hz,4 H)。13C NMR(CDCl3)δ 60.75,35.41,32.08。
2,2'-(亞甲基雙(硫烷二基))二乙醇(比較例2):將2-巰基乙醇(6.00mL,85.4mmol)及粉碎之氫氧化鈉(3.41g,85.4mmol)添加至備有冷凝管,攪拌棒,及滴液漏斗之圓底燒瓶。將此燒瓶放置在冰浴中,而且使燒瓶內容物攪拌。使反應混合物保持在低於20℃時,經由添加漏斗逐滴添加二溴甲烷(2.93mL,42.7mmol)。添加完成後,使反應混合物平衡至室溫,而且於80℃迴流大約2小時。冷卻至室溫後,濃縮混合物至乾燥,然後溶解在最小量的水中,過濾,再濃縮至乾燥。以乙酸乙酯萃取所得之固體,接著濃縮至乾燥,得到呈無色且低熔化固體之比較例2化合物(7.05g,98%)。1H NMR(500MHz,D2O)δ 3.99(s,2 H),3.94(t,J=6.3Hz,4 H),3.00(t,J=6.3Hz,4 H)。13C NMR(126MHz,D2O)δ 60.43,34.65,33.14。
化合物1至12及比較例1和2的溶解度評估如下:稱量25g各化合物至小瓶中,而且添加5mL之17%甲烷磺酸(MSA)/DI水溶液。若化合物溶解,則再另添加25mg(以增量方式)
該化合物直至不再溶解或250mg被溶解在5mL中。結果示於表1。
各種化合物的安定性測定如下:將5mg化合物溶解在1mL之17%MSA/水溶液中,而且放置於玻璃小瓶中。將各玻璃小瓶加蓋,而且放置於在50℃之乾加熱浴中達至三週。定期自乾加熱浴移出各試樣,而且視覺地檢查沉澱的證據。結果示於表1。
使用兩種不同試驗測定化合物6及比較例1之安定性。試驗1中,將溶解在DI水中之化合物6及比較例1之各溶液(5.96mg/mL之濃度)放置在分別之小瓶中。對各小瓶添加MSA水溶液(70%),然後將小瓶加蓋,放置於50℃烘箱中,定期視覺地檢查沉澱物的形成。60小時後,比較例1之溶液顯示大量白色絨毛狀沉澱物。比較上,化合物6之溶液在120小時後藉由視覺檢查沒有顯示沉澱物形成。試驗2中,將溶解在D2O中之化合物6及比較例1之各溶液(5.96mg/mL之濃度)放置在分別之NMR管中。得到各溶液之1H NMR(400MHz)光譜。其次,製備溶解在D2O中之MSA溶液(70%),而且添加至各NMR管中。立刻測量各試樣之第二1H NMR光譜。其次,將NMR管放置於50℃烘箱中,定期移出,藉由1H NMR分析之,再放回烘箱。比較例1顯示在添加MSA溶液時立刻失去1H NMR光譜,而化合物6顯示在7天後1H NMR光譜沒有改變。
安定性測驗中沉澱物的存在係硫化物化合物分解的證據。由上述數據可看出,本案之硫化物化合物具有非常良好的浴安定性。本案之化合物6及7的安定性顯著地優於比較例1及2者。令人意想不到地發現本案之硫化物化合物中在對硫原子而言為至少γ之碳原子上之羥基取代(亦即,離硫原子3個或更多個碳之羥基)提供顯著改良之銀及銀-合金電鍍浴的安定性。
重複實施例1至10之一般程序以製備下述硫化物化合物。
藉由組合75g/L來自甲烷磺酸錫之錫,0.4g/L來自甲烷磺酸銀之銀,275mL/L之70%甲烷磺酸,4g/L乙氧基化雙酚A(13個環氧乙烷單元)作為界面活性劑,1g/L乙基麥芽醇,50mg/L五羥基黄酮,1g/L氫醌單磺酸鉀鹽,作為錯合劑之硫化物化合物,及DI水(其餘量)製備錫-銀(Sn-Ag)電鍍浴。表3顯示所使用之錯合劑及其用量。Sn-Ag浴13-C使用來自美國專利第6,998,036及7,628,903號之習知錯合劑。
錫-銀晶圓凸塊化測驗:在NeXX鍍覆工具中使用各上述Sn-Ag電鍍浴將Sn-Ag焊料凸塊電鍍在200mm經圖案化之矽晶圓上。此經圖案化之晶圓具有75μm直徑通孔和3種不同間距尺寸(150,225和375μm),3至20%之可鍍覆面積,75μm之負乾膜光阻高度,及1 k Å Ti/3k Å Cu之種子(seed)。使用具有5μm高度之銅柱體做為UBM層,以提升Sn-Ag焊料凸塊與晶圓間之黏合性。利用快速振盪垂直地鍍覆晶圓。使用鍍覆化之鈦作為不可溶陽極,及使用12至20A/dm2之電流密度。
使用輪廓儀(KLA Tencor)在各晶圓上測量11個凸塊的高度,以得到晶粒內(WID)均勻度(或共面度),其係以方程式1計算之:
式中,hmax為晶粒中最高Sn-Ag凸塊的高度,hmin為晶粒中最矮Sn-Ag凸塊的高度,及havg為Sn-Ag焊料凸塊的平均高度。共面度值(或晶粒內均勻度)愈小,Sn-Ag焊料凸塊愈均勻。對確保元件適當貼附至晶圓而言,焊料凸塊的均勻度是關鍵。
使用上述所製備之各電鍍浴在晶圓上沉積錫-銀層。分析錫-銀沉積物以測定共面度%(晶粒內均勻度)及迴銲後之孔洞的形成。所得之焊料凸塊的分析結果示於表4。
由上述數據可看出,本硫化物化合物可使用作為銀電鍍浴中之錯合劑,提供無孔洞之沉積物。
在常溫儲存2週後,Sn-Ag電鍍浴13-1,13-2及13-3皆無顯示硫化物化合物錯合劑之任何分解或沉澱。
重複實施例15之程序,但使用下述界面活性劑及硫化物化合物錯合劑。界面活性劑A為下式之烷氧基化胺氧化物:
式中Ra為(C9-C11)烷基,及界面活性劑B為具有20% EO基團,80% PO基團且2000之平均分子量之EO/PO/EO共聚物(Pluronic L61)。
Claims (10)
- 一種電鍍組成物,包括:浴可溶之銀離子來源;水;酸電解質;及下式之硫化物化合物:Y1-(CR1R2)m-S-(CR3R4)x-S-(CR5R6)n-Y2式中,Y1及Y2獨立選自CO2H,SO3H,PO3H2,CONR7R8及OH;各R1,R2,R5及R6獨立選自H,(C1-C6)烷基,CO2H,及經羥基取代之(C1-C6)烷基;各R3及R4獨立選自H及(C1-C6)烷基;m=1至6;n=1至6;R7及R8獨立選自H及(C1-C3)烷基;及x=1至6;但當Y1=OH時,m=3;限制條件為當Y2=OH時,n=3;以及限制條件為當R1,R2,R5及R6之任一者為經羥基取代之(C1-C6)烷基時,該羥基係鍵結於對硫原子而言為至少γ之碳原子。
- 如申請專利範圍第1項所述之組成物,進一步包括浴可溶之錫離子來源。
- 如申請專利範圍第1項所述之組成物,其中各R1,R2,R5及R6獨立選自H,(C1-C4)烷基,CO2H,及經羥基取代之(C1-C4)烷基。
- 如申請專利範圍第1項所述之組成物,其中Y1及Y2獨立選自CO2H,SO3H,及PO3H2。
- 如申請專利範圍第1項所述之組成物,其中m=1至4。
- 如申請專利範圍第1項所述之組成物,其中n=1至4。
- 如申請專利範圍第1項所述之組成物,其中Y1與Y2相同。
- 如申請專利範圍第1項所述之組成物,其中Y1及Y2獨立選自CO2H,SO3H,及OH;各R1,R2,R5及R6獨立選自H,(C1-C3) 烷基,及經羥基取代之(C1-C3)烷基;各R3及R4獨立選自H及(C1-C3)烷基;m=1至4;n=1至4;及x=1至4。
- 如申請專利範圍第1項所述之組成物,進一步包括下式之烷氧基化胺氧化物界面活性劑:
- 一種沉積錫-銀層之方法,包括:使基板與申請專利範圍第1項所述之組成物接觸;施加一段時間的電位,以在基板上沉積含銀之層。
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JP2013216975A (ja) | 2013-10-24 |
TWI525223B (zh) | 2016-03-11 |
US20130256145A1 (en) | 2013-10-03 |
SG193763A1 (en) | 2013-10-30 |
CN103361683B (zh) | 2016-08-10 |
US8980077B2 (en) | 2015-03-17 |
KR102055598B1 (ko) | 2019-12-13 |
DE102013005499B4 (de) | 2016-10-06 |
DE102013005499A1 (de) | 2013-10-02 |
KR20130111454A (ko) | 2013-10-10 |
CN103361683A (zh) | 2013-10-23 |
JP6141664B2 (ja) | 2017-06-07 |
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