TWI553753B - 用於微電子裝置之可引線接合之表面 - Google Patents

用於微電子裝置之可引線接合之表面 Download PDF

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TWI553753B
TWI553753B TW101121398A TW101121398A TWI553753B TW I553753 B TWI553753 B TW I553753B TW 101121398 A TW101121398 A TW 101121398A TW 101121398 A TW101121398 A TW 101121398A TW I553753 B TWI553753 B TW I553753B
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palladium
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thickness
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TW201308456A (zh
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艾爾伯奇特 烏利格
喬瑟夫 蓋達
克里斯多夫 蘇誠傳克
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德國艾托特克公司
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Description

用於微電子裝置之可引線接合之表面
本發明係關於半導電基板上用於金屬引線接合施加之金屬及金屬合金層序列。
由諸如矽晶圓等半導電基板製成之微電子裝置在外表面上包括用於在該微電子裝置與IC基板或印刷電路板之間提供電接觸之接觸區域。該等可呈接觸墊或凸塊結構形式之接觸區域通常係由銅、銅合金、鋁或鋁合金組成。為提供該電接觸，施加焊接及引線接合。
在兩種情形下，必須準備接觸區域，以藉由在接觸區域之頂部上沈積金屬或金屬合金層來提供可銲性及可接合性，該等金屬或金屬合金層提供障壁層及第一及/或第二可接合表面之功能。
障壁層在焊接或引線接合期間防止接觸區域與第一及/或第二接合層間之擴散。此外，障壁層藉由提供硬「屏蔽層」向接觸區域下方微電子裝置之敏感部分提供機械保護。此功能在引線接合操作中尤其需要，其中在接合期間將金或銅薄引線壓製至接觸墊上。
US 6,815,789 B2揭示至少一個包括鎳、鈀及其合金中至少一者之層。鎳(合金)層用作障壁層。該鎳(合金)層之厚度應為至少1 μm，以提供充分障壁性質。
US 2001/0033020 A1揭示厚度為0.5 μm至1.5 μm之選自鎳、鈷、鉻、鉬、鈦、鎢及其合金之障壁層。
US 6,445,069 B1揭示厚度在0.5 μm至20 μm範圍內之由鎳製成之障壁層。
個別接觸區域間之距離(表示為「節距」)因微電子裝置之不斷微型化而減小。同時，接觸區域間之橋接(即不期望電接觸)風險隨之增加。橋接係因沈積至接觸區域上之厚障壁層所致。
引線接合與施加至具有可接合表面之接觸區域上之力相關，此乃因在接合期間將引線壓製至該可接合表面上。
當減小障壁層之厚度時，可使該橋接最小化。然而，同時，接觸區域下方之敏感區在引線接合期間之機械保護不再充分且觀察到因引線接合所致之裝置失效。
因此，本發明之目標係提供具有引線可接合表面之金屬及金屬合金層序列，其可降低接觸區域間之橋接風險且同時在引線接合期間向接觸區域下方微電子裝置之敏感區提供充分機械穩定性。
該等目標係利用包括至少一個具有金屬引線可接合表面之金屬及金屬合金層序列之半導電基板來解決，其中該層序列係以下列順序由以下組成：(i)接觸區域，(ii)選自由鈷合金組成之群之障壁層，該鈷合金係選自由Co-M-B、Co-M-P及Co-M-B-P合金組成之群其中M係選自由Mn、Zr、Re、Mo、Ta及W組成之群，且該障壁層之厚度在0.03 μm至0.3 μm範圍 內，及(iii)第一接合層，其係選自鈀及鈀合金且厚度在0.05 μm至0.3 μm範圍內。
三元或四元鈷合金更佳係選自由以下組成之群：Co-Mo-P、Co-W-P、Co-Mo-B、Co-W-B、Co-Mo-B-P及Co-W-B-P合金。
本發明之金屬及金屬合金層序列因障壁層之厚度較小而降低橋接風險。同時，該金屬及金屬合金層序列在金屬引線接合操作期間提供充分機械穩定性以防止損害接觸區域下方之敏感區。
通常藉由用酸清潔劑預處理來準備接觸區域之銅或銅合金表面以用於鍍敷障壁層，且隨後在微蝕刻浴液中減少表面銅氧化物。出於此目的，通常在氧化酸性溶液(例如硫酸及過氧化氫之溶液)中實施蝕刻清潔。較佳地，此後為酸性溶液(例如硫酸溶液)中之另一清潔。
對於鋁及鋁合金之預處理而言，可利用滿足無氰離子之化學工業標準之不同鋅活化劑(zincation)，例如Xenolyte®清潔劑ACA、Xenolyte® Etch MA、Xenolyte® CFA或Xenolyte® CF(皆購自Atotech Deutschland GmbH)。該等用於鋁及鋁合金之預處理方法揭示於(例如)US 7,223,299 B2中。
出於本發明目的，在沈積三元或四元鈷合金擴散障壁層之前，向接觸區域施加額外活化步驟可能有用。該活化溶 液可包括產生薄鈀層之鈀鹽。該層極薄且通常不會覆蓋整個銅或銅合金引線接合部分。並不認為該層係層總成之不同層，而是形成金屬晶種層之活化。該晶種層之厚度通常為數埃(angstrom)。藉由浸泡交換製程將該晶種層鍍敷至銅或銅合金層上。
接下來，藉由無電鍍敷將選自Co-M-P、Co-M-B及Co-M-B-P合金之三元或四元鈷合金沈積至經活化接觸區域上。M係選自包括Mn、Zr、Re、Mo、Ta及W之群。更佳地，M係選自由Mo及W組成之群。
三元或四元鈷合金之厚度在0.03 μm至0.3 μm、更佳0.05 μm至0.25 μm範圍內。
三元或四元鈷合金較佳係選自由以下組成之群：Co-Mo-P、Co-W-P、Co-Mo-B、Co-W-B、Co-Mo-B-P及Co-W-B-P合金，且最佳係選自Co-Mo-P及Co-W-P合金。
適宜鈷合金鍍敷溶液包括鈷鹽及諸如以下等還原劑：次磷酸或其選自次磷酸鈉、次磷酸鉀及次磷酸銨之浴液溶性鹽。此溶液較佳應不含能形成不溶性亞磷酸鹽之鹼金屬離子或鹼土金屬離子。其他適宜鍍敷浴液包括選自以下之還原劑：硼烷化合物或硼烷與次磷酸鹽化合物之混合物。
在使用次磷酸鹽化合物作為還原劑之情形下，獲得Co-M-P合金沈積物。硼烷化合物還原劑產生Co-M-B合金沈積物及次磷酸鹽與硼烷化合物之混合物，此乃因該還原劑產生Co-M-B-P合金沈積物。
鍍敷浴液進一步含有M離子源。適宜源係選自包括水溶 性鉬酸鹽及鎢酸鹽(例如Na2MoO4及Na2WO4)之群。添加至鍍敷浴液中之M離子之量在5 g/l至20 g/l、更佳8 g/l至12 g/l範圍內。
在無電鈷合金溶液中，操作性鈷離子濃度通常為1 g/l至18 g/l、較佳3 g/l至9 g/l。
鍍敷浴液中所用還原劑之量係在2 g/l至60 g/l、更佳12 g/l至50 g/l且最佳20 g/l至45 g/l範圍內。對於習用實踐而言，在反應期間補充還原劑。
錯合劑係以高達200 g/l、更佳15 g/l至75 g/l之量採用。
在一項實施例中，選擇羧酸、多胺或磺酸或其混合物作為錯合劑。有用羧酸包含單-、二-、三-及四-羧酸。羧酸可經由多個取代基部分(例如羥基或胺基)取代，且該等酸可以其鈉、鉀或銨鹽形式引入鍍敷溶液中。一些錯合劑(例如乙酸)亦可用作緩衝劑，且該等添加組份針對任一鍍敷溶液之適當濃度可根據該等組份之雙重功能進行最佳化。
該等用作錯合劑之羧酸之實例包含：單羧酸，例如乙酸、羥基乙酸(乙醇酸)、胺基乙酸(甘胺酸)、2-胺基丙酸(丙胺酸)；2-羥基丙酸(乳酸)；二羧酸，例如琥珀酸、胺基琥珀酸(天冬胺酸)、羥基琥珀酸(蘋果酸)、丙二酸(propanedioic acid,malonic acid)、酒石酸；三羧酸，例如2-羥基-1,2,3丙烷三甲酸(檸檬酸)；及四羧酸，例如乙二胺四乙酸(EDTA)。在一項實施例中，利用兩種或更多種上述錯合劑之混合物。
水性無電鍍敷浴液可在上述pH範圍內操作。由於鍍敷溶液具有在其操作期間因形成氫離子而變得酸性較強之傾向性，因此可藉由添加浴液溶性且浴液相容性鹼性物質(例如鈉、鉀或銨之氫氧化物、碳酸鹽及碳酸氫鹽)來週期性地或連續地調節pH。可藉由以高達30 g/l、更佳2 g/l至10 g/l之量添加多種緩衝化合物(例如乙酸、丙酸、硼酸或諸如此類)來改良鍍敷溶液之操作pH之穩定性。
無電鍍敷溶液亦包含業內迄今已知類型之有機及/或無機穩定劑，包含可以諸如乙酸鹽等浴液溶性且相容性鹽之形式方便地引入之鉛離子、鎘離子、錫離子、鉍離子、銻離子及鋅離子。用於無電鍍敷溶液中之有機穩定劑包含含有硫之化合物，例如，硫脲、硫醇、磺酸鹽、硫氰酸鹽等。該等穩定劑係以諸如佔溶液之0.05 ppm至5 ppm等少量使用，且更佳係以0.1 ppm至2 ppm或3 ppm之量使用。
欲鍍敷之基板係在至少40℃至高達溶液沸點之溫度下與鍍敷溶液接觸。在一項實施例中，在70℃至95℃之溫度下且更佳在80℃至90℃之溫度下採用酸性類型之無電鍍敷浴液。鹼性側上之無電鍍敷浴液通常在寬操作範圍內但通常在低於酸性無電鍍敷溶液之溫度下操作。
無電鍍敷溶液與所鍍敷基板之接觸持續時間隨所沈積鈷合金之期望厚度而變化。通常，接觸時間可在5分鐘至10分鐘範圍內。
在鈷合金沈積期間，通常採用溫和攪拌，且此攪拌可係溫和空氣攪拌、機械攪拌、藉由泵送之浴液循環、欲鍍敷 基板之旋轉等。亦可使鍍敷溶液經受週期性或連續性過濾處理以減少其中污染物之含量。在一些實施例中，亦可週期性或連續性地補充浴液組份，以將組份之濃度(且具體而言，鈷離子及M離子及次磷酸根離子之濃度)以及pH值維持在期望範圍內。
然後較佳用水沖洗基板。
接下來，將鈀或鈀合金層沈積至三元或四元鈷合金層上。
本發明鈀層係鈀含量超過99.0重量百分比、較佳超過99.5重量百分比鈀或甚至超過99.9重量百分比或超過99.99重量百分比鈀之層。該鈀層在本文中表示為純鈀層。
在該方法之另一實施例中，鍍鈀層包括90 wt.%鈀至99.9 wt.%鈀及0.1重量百分比磷及/或硼至10.0重量百分比磷及/或硼之合金層。
用以沈積純鈀層之適宜化學鍍敷浴液組合物闡述於(例如)US 5,882,736中。該鍍敷浴液含有鈀鹽、一或多種氮化錯合劑及甲酸或甲酸衍生物，但不含次磷酸鹽及/或胺硼烷化合物。該溶液之pH值高於4。較佳地，使用一級、二級或三級胺或多胺作為氮化錯合劑。其係(例如)乙二胺、1,3-二胺基-丙烷、1,2-雙(3-胺基-丙基-胺基)-乙烷、2-二乙基-胺基-乙基-胺及二伸乙基三胺。另外，亦可使用二伸乙基三胺-五-乙酸、硝基-乙酸、N-(2-羥基-乙基)-乙二胺、乙二胺-N,N-二乙酸、2-(二甲基-胺基)-乙基-胺、1,2-二胺基-丙基-胺、1,3-二胺基-丙基-胺、3-(甲基-胺基)- 丙基-胺、3-(二甲基-胺基)-丙基-胺、3-(二乙基-胺基)-丙基-胺、雙(3-胺基-丙基)-胺、1,2-雙(3-胺基-丙基)-烷基-胺、二伸乙基-三胺、三伸乙基四胺、四伸乙基五胺、五伸乙基六胺及該等氮化錯合劑之任何期望混合物。然而，不使用含有硫之化合物與錯合劑一起作為穩定劑。
更佳地，用於以無電方式沈積純鈀層之溶液係水溶液且含有鈀鹽(例如氯化鈀或硫酸鈀)、作為還原劑(如甲酸)之不含次磷酸鹽之化合物、礦物酸(例如硫酸及鹽酸)或礦物鹼(如氫氧化鈉或氫氧化鉀)、錯合劑(如胺化合物，例如乙二胺)及若需要穩定化合物。或者，可使用其他無電鈀及鈀合金沈積溶液及製程，其為業內所熟知且闡述於以下專利中：US 5,292,361、US 4,424,241、US 4,341,846、US 4,279,951及US 4,255,194。
在約45℃至80℃下將鈀或鈀合金鍍敷製程實施1分鐘至60分鐘，獲得厚度在0.05 μm至0.3 μm、更佳0.1 μm至0.2 μm範圍內之鈀或鈀合金鍍敷層。
較佳地，將純鈀沈積至三元或四元鈷合金上。
視情況，將金或金合金薄層鍍敷至用作第二接合層之純鈀或鈀合金層上。
出於此目的，可使用自先前技術已知之無電鍍金電解質。純鈀或鈀合金層之頂部上可選金層之厚度係0.01 μm至0.5 μm、較佳0.05 μm至0.3 μm。可選金層最佳係藉由浸泡製程沈積。無電鍍金用適宜浴液係以商標Aurotech® SFplus購得(T=80℃至90℃；pH=4.5至6.0；浸泡時間=7 分鐘至15分鐘；0.5 g/l至2 g/l Au(呈K[Au(CN)2])。
實例
現在將藉由參考以下非限制性實例來闡釋本發明。
實例1(比較)
藉由無電鍍敷將鎳磷合金沈積至由銅製成之接觸墊上。在沈積後，該鎳磷合金之厚度係1.0 μm且磷濃度係12重量百分比。
然後在500℃下使該基板退火8小時。
銅至鎳磷合金中之擴散性質(且反之亦然)係使用XPS量測結合對該(等)層之燒蝕來測定。
在退火步驟後觀察到鎳磷合金層中之銅含量為3 at.-%至5 at.-%。
因此，薄鎳磷合金層在升高溫度下不會阻止銅擴散。
實例2
藉由電鍍將Co-W-P合金沈積至由銅製成之接觸墊上。在沈積後，該Co-W-P合金之厚度係0.2 μm且磷濃度係3重量百分比。
如實例1中所述實施熱退火及XPS量測。
在熱退火後在Co-W-P合金層中檢測到可忽略量的銅。
因此，薄Co-W-P合金層在升高溫度下可阻止銅擴散。
實例3
藉由電鍍將Co-W-P合金沈積至由銅製成之接觸墊上。在沈積後，該Co-W-P合金之厚度係0.2 μm且磷濃度係3重量百分比。
接下來，將中間鈀層(厚度：0.3 μm)及其後之頂部金層(厚度：0.03 μm)沈積至鈀層上。
使用DVS標準第2811號來測定最終金屬及金屬合金層序列之引線接合性質，該序列係由銅接觸墊、Co-W-P合金層、鈀含量超過99重量百分比之鈀層及金層組成。
使用型號Delvotec 5410 TS接合器及金引線Au-AH3(Hereaus)及接合參數US功率75%(分度標記(非校準標記)，給定TS接合器之特定參數)；25 gf接合力及25 ms接合時間。每墊大小對30個柱形凸塊進行量測。
在接合測試期間測定以下參數：平均值：65.8 g
標準偏差：7.5 g
最小值：55.4 g
剪切剝離：0%
剪切力>35 cN：0%
所有獲得值皆在DVS標準第2811號及其要求之框架範圍內。因此，薄Co-W-P合金係使用鈀/金塗料之引線接合施加之適宜擴散障壁。
圖1顯示在500℃下熱退火8小時後由Ni-P合金障壁層在由銅製成之接觸區域之頂部上組成之金屬及金屬合金層序列之化學元素的分佈。
圖2顯示在500℃下熱退火8小時後由Co-W-P合金障壁層在由銅製成之接觸區域之頂部上組成之金屬及金屬合金層序列之化學元素的分佈。

Claims (8)

  1. 一種半導電基板，其包括至少一個金屬層序列以產生金屬引線可接合表面，其中該層序列係以下列順序由以下組成：(i)接觸區域，(ii)障壁層，其係選自Co-M-B、Co-M-P及Co-M-B-P合金其中M係選自由Mn、Zr、Re、Mo、Ta及W組成之群，且該障壁層之厚度在0.03μm至0.3μm範圍內，及(iii)鈀作為第一接合層，該第一接合層具0.05μm至0.3μm範圍內之厚度且其鈀含量超過99.0重量百分比，其中該純鈀層係由化學鍍敷組合物製得，該化學鍍敷組合物包含鈀鹽、一或多種氮化鋯合劑及甲酸或甲酸衍生物，但不含次磷酸鹽及/或胺硼烷化合物，且具有高於4之pH值，且其中在45℃至80℃下將鈀鍍敷製程進行1至60分鐘。
  2. 如請求項1之半導電基板，其中該障壁層係選自由以下組成之群：Co-Mo-P、Co-W-P、Co-Mo-B、Co-W-B、Co-Mo-B-P及Co-W-B-P合金。
  3. 如請求項1之半導電基板，其中該障壁層之該厚度在0.05μm至0.15μm範圍內。
  4. 如請求項1之半導電基板，其中該第一接合層之該厚度在0.1μm至0.2μm範圍內。
  5. 如請求項1之半導電基板，其中該堆疊進一步包括該第一接合層之頂部上之第二接合層。
  6. 如請求項5之半導電基板，其中該第二接合層係選自由金及金合金組成之群。
  7. 如請求項5或6之半導電基板，其中該第二接合層之厚度在0.02μm至0.1μm範圍內。
  8. 如請求項5或6之半導電基板，其中該等接觸區域係由選自由銅、銅合金、鋁及鋁合金組成之群之金屬組成。
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TW201308456A (zh) 2013-02-16
TW201307187A (zh) 2013-02-16
KR20140043753A (ko) 2014-04-10
KR102004555B1 (ko) 2019-07-26
EP2535929A1 (en) 2012-12-19
WO2012171727A1 (en) 2012-12-20
CN103597595A (zh) 2014-02-19
US20140110844A1 (en) 2014-04-24
TW201305396A (zh) 2013-02-01
US9076773B2 (en) 2015-07-07
JP2017123466A (ja) 2017-07-13

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