TWI467675B - 用於改善打線製程的引線架清潔方法 - Google Patents

用於改善打線製程的引線架清潔方法 Download PDF

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TWI467675B
TWI467675B TW101114791A TW101114791A TWI467675B TW I467675 B TWI467675 B TW I467675B TW 101114791 A TW101114791 A TW 101114791A TW 101114791 A TW101114791 A TW 101114791A TW I467675 B TWI467675 B TW I467675B
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acid
weight
composition
lead frame
contacting step
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TW101114791A
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TW201308455A (zh
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Terence Quintin Collier
David Barry Rennie
Rajkumar Ramamurthi
Gene Everad Parris
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Air Prod & Chem
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    • H01L21/4835—Cleaning, e.g. removing of solder
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    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Description

用於改善打線製程的引線架清潔方法 相關申請案之相互參照
本案請求2011年4月25日申請的美國臨時申請案第61/478,582號的優先權，在此以引用的方式將其全文併入本文。
本發明係關於一種用於清潔半導體晶片及引線架上的金屬表面以改善打線製程之方法。特別是，本發明係關於一種使該等金屬表面暴露於一水性清潔溶液以從該等晶片和引線架的金屬表面除去金屬氧化物、污染物及其他殘餘物之方法。
在製造半導體裝置的期間，引線架在傳統上用作能同時安裝及處理多數半導體晶粒或晶片的有成本效益方式。各自引線架通常具有多數供安裝該等晶片用的晶粒墊。該引線架也扮作經由該引線架的引線把該晶片電連接至外部裝置的機構。在習稱為打線的製程中把接合導線(bonding wire)連至該晶片上的電氣接點和該引線架的上述引線。該等焊墊通常由鋁構成但是其也可為銅。該等導線的另一端附接於該引線架上的接點引線(可為銀、金等等)。
圖1中描繪用於製造相關零件中之晶粒封裝件的典型習知方法。首先，於步驟10，從已經形成晶粒的晶圓上裁 切或鋸切晶粒。等該晶粒從該晶圓切下之後，在晶粒接合或晶粒附接步驟12中將該晶粒背側牢固地附接於一載具或引線架。典型地，在該晶粒接合步驟12中，使用有機黏著劑，例如環氧樹脂將該晶粒附接於該引線架及接著藉由烘焙使其固化。一旦該環氧樹脂固化後，在步驟14中將該晶粒接合於該引線架。
上述將該等金屬導線連接於該等焊墊和接點的製程叫做“打線”。打線時會發生的一個問題是該等金屬導線無法黏於該等焊墊及/或該等接點。該等導線與該等焊墊/接點之間的差黏附力可能有幾個成因像是，舉例來說，該等金屬表面被氧化；及該等金屬表面上有污染物。該等導線與該等焊墊/接點之間的差黏附力會經由諸如NSOP(焊墊不黏；No stick on pads)、NSOL(引線不黏；Non stick on leads)、短尾(short tails)、球脫落(lifted ball)缺陷、差的金屬間化合物均勻性、焊墊彈坑、形成空穴等等的機制直接或間接造成製程失敗。這些不僅導致沒有效率的打線製程，而且還造成差的裝置可靠度。為了改善黏附力，打線之前必須清潔該等金屬表面。
過去，在該打線步驟14之前，藉由，舉例來說，對該引線架和附接的晶粒施以氬電漿而清潔該晶粒的正面。然而，此氬電漿製程有幾個缺點。舉例來說，氬電漿製程無法徹底清潔銅和鋁焊墊上的殘餘物和微粒。另外，該氬電漿製程無法從焊墊有效率地除去氧化銅或氧化鋁。至於最後的實例，該氬電漿製程無法從鋁焊墊有效率地除去其 他污染物例如氟，而不會損及處理過的組件。因此，需要一種不會遇到上述缺點而清潔打線製程所涉及的金屬表面像是，舉例來說，導線、焊墊及引線架接點，的方法。
本發明藉由提供一種處理引線架組合件以除去不欲的材料或預備供隨後打線用的引線架組合件表面之方法滿足此需求，其中引線架組合件包含一或更多下列零件或組件：引線架、晶粒、有焊墊在上面的晶粒、接點、接點引線(contact lead)及導線，該方法包含使該引線架組合件的至少一部分或該引線架組合件的多個零件與包含水和至少一酸或至少一鹽的組合物接觸的步驟。該接觸步驟所用的組合物可包含0.003至約25重量%的一或更多羧酸類。
一種處理引線架組合件或包含引線架和一或更多下列零件或組件清單的至少一者的基材之方法：晶粒、焊墊、晶粒附接材料、塑模化合物(mold compound)、接點及導線，該方法包含下列步驟：使該引線架組合件(半導體基材)或其一部分與包含以下，基本上由以下組成，或由以下組成的組合物接觸：酸緩衝液，其具有按照介於10：1至1：10的酸對鹽(舉例來說銨鹽)莫耳比之選自羧酸或多元酸的酸及該酸的鹽(舉例來說銨鹽)；及任意有機極性溶劑，其可依所有比例混溶於水；及任意氟化物和水，其中在一些具體實施例中該組合物具有介於約3至約7的pH，及其中該引線架可包含在至少一表面上的鋁金屬；而且該方法可 包含乾燥該半導體基材的附帶步驟。
在另一形態中，本發明提供一種處理半導體基材或引線架組合件或基材以除去不欲的材料或預備供隨後打線用的引線架組合件表面之方法，其中該引線架組合件包含一引線架，該引線架包含一或更多下列組件清單的至少一者：晶粒、焊墊、晶粒附接材料、塑模化合物、接點及導線，該方法包含下列步驟：使該引線架或該引線架的一部分與包含以下，基本上由以下組成，或由以下組成的組合物接觸：約0.005至約16重量%的至少一羧酸、其鹽或其混合物或含胺基的羧酸、其鹽或其混合物；約0.003至約4重量%的至少一羥基羧酸、其鹽或其混合物或含胺基的羧酸、其鹽或其混合物；而且剩餘部分實質上為水，並且具有約1至約4的pH，其中該半導體基材包含在至少一表面上的銅金屬；及乾燥該半導體基材。在一些具體實施例中，較佳為二羧酸類。
在又另一形態中，本發明提供一種處理包含引線架的引線架組合件之方法，上述方法包含：把一或更多個別晶粒附接於包含接點引線的引線架以形成具有暴露的(舉例來說，鋁、銅、Ni、Pd、Au、Ag及Mg)金屬表面的組合件；使該引線架組合件與包含以下，基本上由以下組成，或由以下組成的組合物接觸：酸緩衝液，其具有按照介於10：1至1：10的酸對鹽(舉例來說銨鹽)莫耳比之選自羧酸或多元酸的酸及該酸的鹽(舉例來說銨鹽)；及任意有機極性溶劑(其可依所有比例混溶於水)；及任意氟化物和水，其中 該組合物可具有介於約3至約7的pH；乾燥該基材；進行打線步驟，其包含將導線附接於該等晶粒上的焊墊與該引線架上的接點引線之間以形成一晶粒及引線架組合件；及在該晶粒及引線架組合件上面形成塑模以形成一封裝電路。
在又再另一形態中，本發明提供一種處理包含引線架的微電子裝置基材之方法，上述方法包含：把個別晶粒附接於包含接點引線的引線架以形成具有暴露的鋁金屬表面的基材；使該半導體基材與包含以下，基本上由以下組成，或由以下組成的組合物接觸：約0.005至約16重量%的至少一二羧酸、其鹽或其混合物；約0.003至約4重量%的至少一羥基羧酸、其鹽或其混合物或含胺基的羧酸、其鹽或其混合物；而且剩餘部分實質上為水，並且具有約1至約4的pH；乾燥該基材；進行打線步驟，其包含將導線附接於該等晶粒上的焊墊與該引線架上的接點引線之間以形成一晶粒及引線架組合件；及在該晶粒及引線架組合件上面形成塑模以形成一封裝電路。
本發明的其他形態、特徵及具體實施例從隨後的揭示內容及附加的申請專利範圍將更加顯而易見。除非另行指明，否則文中所述的所有重量%均以該組合物的總重量為基準。“基本上由...組成”意指該組合物可含有沒在申請專利範圍的組件，只要是用於相同清潔製程時那些沒在申請專利範圍的組件加於不同申請專利範圍內的清潔組合物不會實質上衝擊到金屬氧化物從該引線架組合件的焊墊的移 除即可。金屬氧化物從該引線架組合件的移除速率較佳是約2 Å/min或更高。以上的氧化物移除速率並非試圖表示該引線架清潔製程的限制。例如，在批次清潔製程中可將許多引線架浸於含有文中所述的清潔溶液之清潔浴中，其中能經歷長時間，例如100分鐘給予1-2 Å/min的氧化物移除速率，而且仍能獲得乾淨的引線架。
本發明另外提供可用於文中所述的方法的引線架清潔組合物。
本發明關於用於處理微電子裝置基材及封裝件的組合物，其包括可用於打線製程期間將金屬導線從焊墊連至引線架的過程中製備金屬表面的組合物。該措辭“引線架”可用使用；但是其不代表有限制並且包括所有類型的半導體封裝基材，例如，經鍍敷或未經鍍敷的BGA及有機基材及引線架。本發明也關於處理引線架組合件以除去不欲的材料或預備供隨後打線用的引線架組合件或半導體基材的表面之方法。該措辭“引線架組合件”或“引線架基材”可用以意指；但是其不代表有限制，任何類型的引線架，其被至少一或更多晶粒接合並且也可包含其他組件，該等組件屬於該引線架的一部分，附接(例如，接合或焊接)於該引線架。
為了便於引用，"微電子裝置"相當於半導體基材及封裝件、平板顯示器及微電機系統(MEMS)，其製造是為了用 於微電子裝置、積體電路或電腦晶片應用。咸能理解該措辭"微電子裝置"不表示以任何方式限制並且包括任何最終將變成微電子裝置或微電子組合件的基材。較佳地，該微電子裝置包含引線架組合件或半導體基材。
用於本文時“羧酸”意指(除非另行指明或從上下文顯而易見)單-、二-或聚-羧酸，其包括含胺基的單-、二-或聚-羧酸類、其鹽類或其混合物，包括含羥基的單-、二-或聚-羧酸類、其鹽類或其混合物及/或含其他基團的單-、二-或聚-羧酸類。
用於本文時，該措辭"半導體基材"包括任何基材或部分形成的封裝件，其最終將變成微電子裝置或微電子組合件。較佳地，該半導體基材包含含附接於引線架的晶粒的引線架組合件。
用於本文時，"約"意思是相當於設定值的±5%。
用於本文時，關於從上面具有上述污染物(包括金屬氧化物)的微電子裝置清潔污染物的"適合性"相當於從該微電子裝置，更明確地說該引線架組合件或該引線架組合件的零件，舉例來說，該晶粒或該晶粒上的焊墊，至少部分除去上述殘餘物/污染物。較佳地，使用本發明的組合物及方法從該微電子裝置，更明確地說該引線架組合件或該引線架組合件的零件，舉例來說，該晶粒或該晶粒上的焊墊，除去至少90%的殘餘物/污染物，更佳地，除去至少99%的殘餘物/污染物。
由於電氣性能及成本的優點使得利用銅或鋁互連件 金屬化技術製作積體電路變得很受歡迎。為了防止金屬間相，給ICs裝設銅或鋁墊。帶有晶片載體或引線架的IC之打線經常使用金和銅導線材料，但是鋁和銀也有人使用。把這些導線接合於不同墊材料產生不同的冶金系統。最近有一個從金轉往銅導線的趨勢，其主要的動機是因為成本低相當多。
不幸的是，銅和鋁二者均氧化得非常迅速，於是更難以達成可靠的導線接合。因此，為了確保該導線接合的接合性及可靠度，關鍵條件之一是該接合面理應沒有或實質上沒有任何污染物，包括氧化物在內。通常於一個位置處在單一晶圓上形成多重電路及接著將該等晶圓運送至另一個位置，在那裡從該晶圓切成晶粒並且封裝起來。因為在該晶圓加工及封裝製程之間可能經過相當長時間，所以在此時期會發生該等晶粒上的銅或鋁焊墊氧化。因此，本發明提供在該電路製作於晶圓上之後，但是在該晶粒已經包封或完全封裝之前有效地清潔積體電路的銅和鋁墊。
現在參照圖2，一種製造半導體晶圓的方法，有多數積體電路形成於該半導體晶圓上。該等積體電路可能有銅或鋁所形成的焊墊。在矽晶圓上形成帶有此類墊子的電路的方法已經知道而且對於本發明的理解並不需要其詳細討論。咸瞭解在該晶圓上形成積體電路之後進行本發明的方法。一般，這是在所有層都已經施敷於該晶圓及該晶圓已經於去離子水中沖洗及該晶圓背面已經磨過以除去不需要的材料之後。其後，於試驗/組裝/封裝設施處處理該晶圓， 其中各自晶片或晶粒的測試係於仍呈晶圓形態時進行；於這個習稱為晶圓級試驗(WAFER LEVEL test)的步驟時，確認是良好的晶粒。該晶圓接著藉由切割製程來切割或單片化。已經確定通過該晶圓級試驗的各自所得的晶片或晶粒(“習稱良好晶粒”)可藉由晶粒附接處理步驟附接於一引線架，該晶粒附接處理步驟包括施敷環氧樹脂、焊膏或其他黏著性材料於一引線架及/或表面，該表面可能是晶粒的背面，及將該晶粒附接於該引線架。該引線架可具有焊料凸塊或柱形凸塊或形成在上面的類似附接零件以安放該晶粒並且將環氧樹脂、焊膏或其他黏著性材料施敷或安放在上面。通常，引線架，其可呈長條或連續帶/捲狀，含有許多其後將形成於封裝件中的附接晶粒。若施敷環氧樹脂，該引線架或基材可接著於高溫製程中進行環氧樹脂固化以確保該晶粒適當黏附於該基材。若是使用焊膏，則隨後接著焊接步驟。其後，用導線連於該晶粒上的焊墊與該引線架上的接點之間。這些引線架或引線架組合件(其後)將會被單片化以形成要被塑模及包封的個別封裝件。本發明係關於該引線架組合件上進行的清潔，其可能在高溫環氧樹脂固化或其他晶粒附接步驟之後，及在打線之前發生，並且用於從金屬焊墊及引線架或基材接點及表面除去氧化物及其他污染物。
現在參照圖2，顯示一種製備半導體晶圓的方法，有多數積體電路形成於該半導體晶圓上。該等積體電路可具有由銅或鋁所形成的焊墊。在矽晶圓上形成帶有此類墊子 的電路的方法已經知道而且對於本發明的理解並不需要其詳細討論。咸瞭解在該晶圓上形成積體電路之後進行本發明的方法。一般，這是在所有層都已經施敷於該晶圓及該晶圓已經於去離子水中沖洗及該晶圓背面已經磨過以除去不需要的材料之後，再者，較佳是在進行各自晶片或晶粒的測試之後。通常，在測試之後及切割之前進行，該晶圓將再利用溶劑例如去離子水、異丙醇、丙酮及甲醇清潔。本發明係關於在該晶圓通常已經進行測試、切割之後及該引線架組合件形成之前或之後進行的清潔，並且用於從該等金屬焊墊除去氧化物，及接著把導線附接於該等焊墊。經過那些步驟之後，可接著在該引線架組合件上模塑出封裝件的步驟，其典型處於真空之下。儘管圖2沒顯示，但是本發明的方法包括正好在該引線架組合件形成之前進行該清潔步驟，然後接著該引線架組合件的形成(也就是說，把該晶粒附接於該引線架)，然後接著把該等導線附接於該等焊墊的方法。
更明確地說，於步驟20開始，將其分成步驟20A及步驟20B，使該晶圓及特別是各自晶粒的金屬焊墊與兩種清潔組合物(組合物A或組合物B)之任一者所示的清潔組合物接觸，該二清潔組合物將更詳細描述於下文。(圖2中的方法顯示可具有單一清潔步驟。)較佳地，本發明方法的清潔步驟包含使該引線架組合件或該引線架組合件的至少一部分，例如該等晶粒或可能已經附接於該引線架的晶粒上的焊墊，與組合物A(較佳是用於含鋁的基材)或組合物B (較佳是用於含鋁或含銅的基材)任一者接觸。該引線架組合件的至少一部分較佳是於室溫或提高溫度下浸於包含該組合物的浴中經歷約1分鐘至約40分鐘之間的期間，較佳是約5分鐘至約30分鐘，及更佳是約20至約30分鐘。
用以清潔該引線架組合件的焊墊的組合物包含含酸的水溶液，較佳是一或更多羧酸類或多元酸類，的水溶液。該組合物可包含水和約0.003重量%至約25重量%的一或更多酸類。該組合物的一些具體實施例可具有1至7的pH。在一些具體實施例中，該組合物包含一酸緩衝液；該酸是該酸緩衝液的一部分。在其他具體實施例中，該組合物包含一或更多羧酸類。該組合物可包含一或更多酸類，及/或一或更多溶劑及/或一或更多氟化物(也稱作含氟的化合物)及/或一或更多添加物。該等添加物可包含界面活性劑及/或腐蝕抑制劑。舉例來說，本發明方法可用的組合物的一些具體實施例包含檸檬酸及任意界面活性劑。該組合物的一些具體實施例可包含除一或更多酸類以外，0%或30重量%至90重量%的有機極性溶劑；0.0005重量%至20重量%的氟化物；0.5重量%至40重量%水；至多15重量%的任意腐蝕抑制劑及/或界面活性劑。本發明方法可用的一些組合物的實例包含水、醋酸或檸檬酸、氟化銨及二甲乙醯胺及任意丙二醇及任意腐蝕抑制劑。
組合物A能用以表示包含酸緩衝液之本發明方法用於清潔引線架組合件的那些組合物。組合物B能用以表示不包含酸緩衝液之本發明方法用於清潔引線架組合件的那些 組合物。
組合物A
在本發明之一具體實施例，該清潔組合物是組合物A。組合物A是包含酸緩衝液及水的清潔組合物並且也可包含極性溶劑(其較佳可依所有比例混溶於水)及/或氟化物。在某些具體實施例中，把該組合物調調節至介於約3至約7的pH而且任意包括腐蝕抑制劑及/或其他添加物。組合物A的一些具體實施例可能不含腐蝕抑制劑，及/或不含添加物及/或不含界面活性劑及/或不含溶劑。屬於該酸緩衝液的一部分的酸較佳包含羧酸及/或多元酸。
較佳地，組合物A包含依照獲得帶有介於3至7的pH之組合物所需的量之酸緩衝液；0重量%至90重量%或30重量%至90重量%的有機極性溶劑，其可依所有比例混溶於水；0.001重量%至20重量%的氟化物；0.5重量%至40重量%水；及至多15重量%的腐蝕抑制劑(及/或其他添加物)。在替代具體實施例中，該組合物可包含至多90重量%或高於90重量%水。
如上所述，文中所述的組合物A包括酸緩衝液。該酸緩衝液，當加於文中所揭示的組合物時，提供pH被調節到使敏感性金屬例如鋁、銅、鈦等等的腐蝕減至最低限度的緩衝組合物。該酸緩衝液係依照獲得預期供該組合物用的pH範圍所需的量添加。用於本文時該措辭“酸緩衝液”，是能抵抗酸或鹼少許加於該組合物造成的pH變化的溶液。該 等酸緩衝液加於文中揭示的組合物防止水的稀釋或被鹼類或酸類污染所引起的pH變動。
為了於該組合物內提供此緩衝效應該酸緩衝液中的酸對其共軛鹼之莫耳比介於10：1至1：10，或實質上1：1，或1：1，其中實質上意指等莫耳濃度的±2重量%。緩衝劑通常被認為是弱酸類而且對於酸或鹼任一者的最廣大緩衝範圍是在該弱酸基團的pka任一側的約1個pH單位。調定該緩衝劑的pH可藉由使酸對鹼的莫耳比介於10：1至1：10或實質上1：1的該酸和該酸的共軛鹼(或在某些具體實施例中質子化鹼)加上預期pH範圍所需的適當pka達成。
此外，具有低於約6的pKa的某些鹽類溶於水時可在有或沒有該酸的情況下使用以製造該等清潔組合物。
在某些較佳具體實施例中，該酸緩衝液含有羧酸或多元酸，例如，磷酸，的銨鹽。示範性酸緩衝液可包括醋酸/醋酸鹽類(例如，銨鹽、胺鹽類等等)、苯甲酸/苯甲酸鹽類(例如，銨鹽、胺鹽類等等)及酚酸/酚酸鹽類(例如，銨鹽、胺鹽類等等)。銨鹽的實例是醋酸或磷酸的銨鹽。有一具體實施例中，該酸緩衝液是醋酸銨和醋酸的水溶液。在又另一具體實施例中，該酸緩衝液是苯甲酸和苯甲酸銨的水溶液。
該組合物可包含0.003至30重量%或0.5至25重量%或0.5至20重量%或0.5至15重量%酸，其係該緩衝劑所用的酸。在某些具體實施例中，該酸緩衝液可含有弱酸例如三羥基苯、二羥基苯及/或水楊羥肟酸。在這些具體實 施例中，弱酸添加量可介於0.003至30重量%或0.5至25重量%或0.5至20重量%或0.5至3重量%。共軛鹼的量是加於該組合物以提供緩衝溶液給該組合物的酸量的函數。
儘管根據本發明的組合物的pH可為1至11，但是在某些具體實施例中，介於約3至約9，或介於約3至約7，或介於約3至約6的pH能讓大部分敏感性金屬鈍化而帶有最低限度的腐蝕。較佳地，該pH範圍為約3至約7。
可加於文中所揭示的組合物的一或更多有機極性溶劑是可與水混溶的那些溶劑。這些溶劑可單獨或依任何組合使用。該等組合物中的一或更多溶劑可以約0重量%至約90重量%，或30重量%至約90重量%，或約30重量%至約70重量%存於其中並且可為可依所有比例混溶於水的有機極性溶劑。有機極性溶劑的實例包括，但不限於，二甲基乙醯胺(DMAC)、單乙醇胺、N-甲基乙醇胺、甲醯胺、N-甲基甲醯胺、γ-丁內酯及N-甲基吡咯烷酮等。還有其他溶劑包括二羥醇類和多羥醇類例如二醇類及多元醇類例如(C2 -C20 )烷二醇類及(C3 -C20 )烷三醇類、環狀醇類及經取代的醇類。其他溶劑包括尿素類，例如二甲基脲及四甲基脲等。這些有機極性溶劑的特定實例是丙二醇、四氫呋喃甲醇(THFA)、二丙酮醇及1,4-環己二甲醇。較佳溶劑包括以下一或多者：二甲基乙醯胺、二甲基脲、丙二醇，其單獨使用或相互合併或與其他溶劑合併使用。
在某些具體實施例中，該有機極性溶劑可為一或更多 甘醇醚類。該等甘醇醚類經常可與水混溶並且可包括甘醇單(C1 -C6 )烷基醚類及甘醇二(C1 -C6 )烷基醚類，例如但不限於，(C1 -C20 )烷二醇類、(C1 -C6 )烷基醚類及(C1 -C20 )烷二醇二(C1 -C6 )烷基醚類。甘醇醚類的實例是乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單異丙醚、二乙二醇單丁醚、二乙二醇單異丁醚、二乙二醇單苯甲醚、二乙二醇二甲醚、二乙二醇二乙醚、三乙二醇單甲醚、三乙二醇二甲醚、聚乙二醇單甲醚、二乙二醇甲基乙醚、三乙二醇甲基乙醚、乙二醇單甲醚醋酸酯、乙二醇單乙醚醋酸酯、丙二醇單甲醚、丙二醇二甲醚、丙二醇單丁醚、丙二醇單丙醚、二丙二醇單甲醚、二丙二醇單丙醚、二丙二醇單異丙醚、二丙二醇單丁醚、二丙二醇二異丙醚、三丙二醇單甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷及2-(2-丁氧基乙氧基)乙醇。甘醇醚類更典型的實例是丙二醇單甲醚、丙二醇單丙醚、三(丙二醇)單甲醚及2-(2-丁氧基乙氧基)乙醇。有一實例是二丙二醇單甲醚，其單獨使用或與本發明所用的組合物中的其他溶劑合併使用。
文中所述的組合物A的組合物中較佳存有氟化物。氟化物，也稱作含氟化合物，包括通式R1 R2 R3 R4 NF所示者，其中R1 、R2 、R3 及R4 係獨立地為氫、醇基、烷氧基、烷基或其混合物。此等化合物的實例是氟化銨(NH4 F)、四甲基氟化銨、四乙基氟化銨、四丁基氟化銨及氟化膽鹼。含 氟化合物還有其他實例包括氟硼酸及氫氟酸。該氟化物較佳是依0.0005或0.001重量%至20重量%或0.1重量%至10重量%的量存在。較佳是氟化銨。在這些具體實施例中，氟化銨可以40%水溶液的形式於市面上購得。
水係呈本發明的組合物的成分並且用於本發明的方法。其可同時呈本發明的其他成分的組分例如氟化銨水溶液或水性酸緩衝液存在，或其可單獨添加。較佳地，水係依0.5重量%至40重量%的量存在。在某些具體實施例中，水的存在可改善氟化銨在本發明的組合物中的溶解度並且有助於污染物的移除。
腐蝕抑制劑可，依至多20重量%的量，加於本發明的組合物。較佳地，抑制劑濃度為約0.5重量%至8重量%。在類似應用的技藝中習知的任何腐蝕抑制劑均可使用，例如美國專利案第5,417,877號所揭示者，在此以引用的方式將其併入本文。在某些具體實施例中，已發現帶有高於6的pKa之抑制劑組合物無法在帶有約3至約6的pH範圍的系統中產生與具有低於約6的pKa之抑制劑組合物一樣的效用。因此，較佳的抑制劑組合物是具有約6或更低的pKa者。腐蝕抑制劑可為有機酸、有機酸鹽、酚、三唑或羥基胺。較佳的抑制劑組合物的實例包括鄰胺苯甲酸、沒食子酸、苯甲酸、鄰苯二甲酸、順丁烯二酸、反丁烯二酸、D,L-蘋果酸、丙二酸、苯二甲酸、順丁烯二酸酐、苯二甲酸酐、羧基苯并三唑、二乙基羥基胺及乳酸及其檸檬酸鹽類等。可用的腐蝕抑制劑的其他實例包括苯磷二酚、第三 丁基苯磷二酚、焦性沒食子酸及沒食子酸酯類。
該組合物也可包括一或更多下列任意添加物：界面活性劑、螯合劑、化學改質劑、染料、生物殺滅劑及其他添加物。該添加物可加到不會負面影響該組合物的pH範圍的程度。代表性添加物的一些實例包括炔醇類及其衍生物、炔二醇類(非離子型烷氧基化及/或自乳化性炔二醇界面活性劑)及其衍生物、醇類、季胺類及二胺類、醯胺類(包括非質子性溶劑例如二甲基甲醯胺及二甲基乙醯胺)、烷基烷醇胺類(例如二乙醇乙胺)，及螯合劑例如β-二酮類、β-酮亞胺類、羧酸類、以蘋果酸及酒石酸為底質的酯類和二酯類及其衍生物，及三級胺類、二胺類和三胺類。在某些具體實施例中，可加於該酸緩衝液組合物的羧酸也可擔任螯合劑的角色。
美國專利案第6,828,289號及美國專利案第7,361,631號中揭示適用於作為本發明的組合物A的配方，在此以引用的方式將其全文併入本文。
組合物B
組合物B能用以表示包含一或更多酸類，但是不包含酸緩衝液之本發明方法用於清潔引線架組合件的那些組合物。
組合物B是不含氟化物或含氟化物的水性組合物。該措辭"不含氟化物"表示至少實質上不含氟化物(例如含有不多於約100 ppb的氟化物)。組合物B可包含約0.003至約 25重量%酸，較佳是一或更多羧酸類及水(於水溶液中)。在一些具體實施例中該組合物可包含約0.003至約25重量%酸、水及至多20重量%的一或更多界面活性劑及/或一或更多腐蝕抑制劑。在一些具體實施例，該界面活性劑包含一或更多含硫的界面活性劑。
在一些具體實施例中，組合物B可包含0.005至約16重量%的至少一羧酸、其鹽類或其混合物，其可為含胺基的羧酸、其鹽或其混合物；及/或約0.003至約4重量%的至少一羥基羧酸、其鹽類或其混合物或含胺基的羧酸、其鹽或其混合物，而且剩餘部分實質上為水，並且具有約1至約4的pH。
在其他具體實施例中，組合物B可包含0.005至約16重量%的至少一二羧酸、其鹽類或其混合物、約0.003至約4重量%的至少一羥基羧酸、其鹽類或其混合物；或含胺基的羧酸、其鹽或其混合物，而且剩餘部分實質上為水，並且具有約1至約4的pH。
典型的羧酸類包括二羧酸類，其包括具有2至6個碳原子者，並且包括草酸、丙二酸、丁二酸、胺基戊二酸、己二酸、順丁烯二酸及反丁烯二酸。較佳的酸是檸檬酸。適合的鹽類包括鹼金屬及銨鹽類。組合物B中可運用包括檸檬酸及草酸及任意丙二酸的混合物。含胺基的二羧酸類的實例包括胺基戊二酸及天門冬酸。
羥基羧酸類的實例包括蘋果酸、酒石酸及檸檬酸。
較佳的羥基羧酸是檸檬酸。適合的鹽類包括鹼金屬及 銨鹽類。
羥基羧酸的較佳鹽是檸檬酸銨。
該含胺基的羧酸可為胺基乙酸、纈草胺酸、丙胺酸及苯基丙胺酸等。
較佳的單羧酸類包括甲酸、乙酸及丙酸類。
在某些具體實施例中，組合物B可另外包含一或更多溶劑，較佳是有機溶劑或有機極性溶劑，較佳是可混溶於水者。這些溶劑可單獨或合併使用。如先前所述可用於組合物A中的所有溶劑均可用於本發明的任何組合物中。供組合物B用的較佳溶劑是，但不限於，二甲基乙醯胺(DMAC)、單乙醇胺、N-甲基乙醇胺、甲醯胺、N-甲基甲醯胺、γ-丁內酯及N-甲基吡咯烷酮等、二羥醇類和多羥醇類例如二醇類及多元醇類例如(C2 -C20 )烷二醇類及(C3 -C20 )烷三醇類、環狀醇類及經取代的醇類、尿素類例如二甲基脲及四甲基脲等。這些有機極性溶劑的特定實例是丙二醇、四氫呋喃甲醇(THFA)、二丙酮醇及1,4-環己二甲醇及丙二醇單甲醚。該溶劑若存在的話較佳依0重量%至60重量%，或0重量%至40重量%，或10重量%至40重量%的量存在。
組合物B可另外包含供組合物A用的上述一或更多氟化物(也就是含氟化合物)。此等化合物的實例是氟化銨、四甲基氟化銨、四乙基氟化銨、四丁基氟化銨及氟化膽鹼。含氟化合物還有其他實例包括氫氟酸。該含氟化合物若是存在的話較佳是依0.0005重量%至20重量%或0.001重量 %至20重量%或0.1重量%至10重量%或0.001重量%至5重量%或0.001重量%至2重量%的量存在。較佳是氟化銨。在一些具體實施例中，氟化銨可以40%水溶液的形式於市面上購得。在包含氟化物的組合物中，較佳是有機溶劑存於其中，但是也有那種有氟化物但是沒有機溶劑的組合物B具體實施例，及其他有有機溶劑但是沒有氟化物存於其中的具體實施例。
除水之外，較佳是去離子水，組合物B也可包括一或更多以下的任意添加物：界面活性劑、生物殺滅劑、腐蝕抑制劑、螯合劑、化學改質劑、染料及其他添加物。添加物之一實例包括至多約0.002重量%的生物殺滅劑的活性部分。典型的生物殺滅劑是Kathan。Kathan包含： 1.2% 5-氯-2-甲基-4-異噻唑啉-3-酮
0.4% 2-甲基-4-異噻唑啉-3-酮
1.1% MgCl2
1.75% Mg(NO3 )2
0.16%三水合硝酸銅 水95.85%。此生物殺滅劑可被用於本發明的任何組合物中。
該添加物可加到不會負面影響該組合物的pH範圍的程度。代表性添加物的一些實例包括界面活性劑例如炔醇類及其衍生物、炔二醇類(非離子型烷氧基化及/或自乳化性炔二醇界面活性劑)及其衍生物、含硫界面活性劑(例如線性烷基苯磺酸酯類(LAS))、直鏈脂肪酸類及/或其鹽類、椰子油脂肪酸衍生物、妥爾油酸(tall oil acid)衍生物、肌胺酸 類、乙醯基化多肽類、二級烷基苯磺酸酯、木質素磺酸酯類、N-醯基-正-烷基牛磺酸酯類、脂肪醇硫酸酯類(FAS)、石化磺酸酯類、二級烷磺酸酯類(SAS)、石蠟磺酸酯類、脂肪醇醚硫酸酯類(FAES)、a-烯烴磺酸酯類、硫代丁二酸酯類、烷基萘磺酸酯類、羥乙基磺酸酯類(isethionates)、硫酸酯類、硫酸化線性一級醇類、硫酸化聚氧乙烯化直鏈醇類、硫酸化甘油三酸酯油類、磷酸酯和聚磷酸酯類及全氟化陰離子型界面活性劑及這些和文中所揭示的任何界面活性劑的混合物及其他習知的界面活性劑、醇類、季胺類和二胺類、醯胺類(包括非質性溶劑例如二甲基甲醯胺及二甲基乙醯胺)、烷基烷醇胺類(例如二乙醇乙胺)，及螯合劑例如β-二酮類、β-酮亞胺類、羧酸類、以蘋果酸及酒石酸為底質的酯類和二酯類及其衍生物，及三級胺類、二胺類和三胺類。在某些具體實施例中，可加於該組合物的羧酸也可擔任螯合劑的角色。添加物可依相對純態或呈水或其他溶劑中的稀釋組分在市面上購得。SAS-10舉例來說可呈水中含10重量%濃度的SAS的形式購得。添加物也可包括早先關於組合物A所述的腐蝕抑制劑；然而，在某些具體實施例中，該等帶高於約4的pKa的抑制劑組合物無法在帶有約1至約4的pH範圍的系統中產生與具有低於約4的pKa之抑制劑組合物一樣的效用。添加的總量，若是存在的話，經常為約0.001至約10，或約0.005至約5，或約0.01至約1重量%。較佳的添加物是一或更多界面活性劑及/或腐蝕抑制劑。在包含羧酸類，界面活性劑及水的具體 實施例中，較佳的界面活性劑是一或更多含硫的界面活性劑。
有一較佳具體實施例包含在關於組合物B之文中所界定的重量範圍中的一或更多酸類、一或更多氟化物、一或更多有機溶劑及一或更多界面活性劑。其他較佳具體實施例是包含在關於組合物B之文中所界定的重量範圍中的一或更多酸類、一或更多氟化物、一或更多有機溶劑及一或更多腐蝕抑制劑的組合物。其他組合物包含水和酸，而且該等氟化物、溶劑及添加物各自為任意組分。
組合物B經常包含高於35重量%水。在沒有溶劑的具體實施例中，組合物B經常包含高於約50，或高於約75，或高於約90，或高於約95.5，或高於約98重量%水。當組合物B包含一或更多溶劑時，組合物B經常包含35至95重量%水或40至90重量%水或45至85重量%水。
該羧酸或二羧酸及/或鹽通常依約0.005至約16重量%，更佳是約0.1至約3重量%及較佳是約0.3至約0.5重量%的量存在。當使用的是酸類的混合物時，實例是草酸和丙二酸的混合物，或檸檬酸和草酸的混合物，每一者經常依約0.003至約8重量%，更常為約0.05至約1.5重量%及較佳是約0.1至約0.3重量%的量存在。
該羥基羧酸若是存於該組合物，通常依約0.003%至約8重量%，更佳是約0.05至約1.5重量%及較佳是約0.1%至約0.3重量%的量存於該組合物中。
運用時，該含胺基的酸例如胺基乙酸若是存於該組合 物中經常依約0.003至約4重量%，更佳是約0.005至約1.5重量%及較佳是約0.005至約0.05重量%的量運用。
儘管根據本發明組合物的pH可為1至11，但是較佳是，關於組合物B，該pH較佳是約1至約4而且更佳是約1至約3，特定實例是約2。該pH經常使用pH試紙或適合的pH參考電極來測量。根據本發明發現要達成本發明的目的該pH是重要的。特別是，該等組合物能除去金屬性和非金屬性微粒狀氧化物，以及二氧化矽；金屬離子污染物例如K、Ca、Ti、Cr、Mn、Fe、Ni、Cu及Zn；吸附於該晶粒或基材上的多種不同硫和氯化物雜質。
本發明的另一特徵是即使是呈濃縮態的組合物也相對安定。例如，可以把包含約0.1至約16重量%及較佳是約6%至約10重量%的二羧酸、約0.05%至約8重量%及較佳是約3%至約5重量%的二羥基羧酸或胺基酸及剩餘部分實質上為水的組合物濃縮物供應並且輸送給最終使用者，為求便利及經濟的緣故該使用者可接著於加工機具處把它稀釋為例如以重量計約19：1稀釋度。
美國專利第6,627,546號及美國專利第7,524,801號揭示適合作為本發明的組合物B的配方，在此以引用的方式將其全文併入本文。
根據本發明的清潔方法使該等金屬表面更乾淨而且，因此，提供該等金屬導線與該等晶粒上的焊墊和引線架接點更好的黏附效果。
再回來引用圖2，等到在步驟20A或20B任一者中使 該基材或該引線架清潔組合件的一部分暴露於(觸及)該清潔組合物之後，乾燥該基材並且進行打線步驟14。該基材可使用可相對於該等引線架組合件運動的周遭空氣或暖空氣任一者，舉例來說藉由市售吹風機，或藉由移動該引線架組合件，予以主動或被動乾燥。或者，該基材可使用壓縮空氣或氣體，例如氮，來乾燥。乾燥時間可變化於數秒至數分鐘。然而，較佳是該基材沒長時期暴露於周遭空氣，因為那會讓該等金屬墊氧化。
以去離子水沖洗的步驟可在該清潔步驟之後及該乾燥步驟之前進行。
一旦該打線完成，於步驟16模塑該基材。較佳地，於步驟16真空封裝該基材。該真空封裝可使用一般知道的商業上可購得的真空封裝設備進行。該基材較佳是在由無反應性材料製造的防震容器中封裝。
顯而易見的是，本發明提供以金屬墊製備晶粒的方法以致於當該等晶圓上的晶粒備妥要封裝時，該等金屬墊有較少氧化及其他污染物及因此該等墊子的打線產生更可靠的接合。本發明另外提供一種在該晶粒封裝製程時以金屬焊墊製備晶粒的方法，其減少該等金屬焊墊上的氧化及其他污染物所以該等墊的打線產生更可靠的接合。咸明白，本發明係關於製備供打線用的金屬焊墊，例如，舉例來說，銅及鋁墊。本發明不限於使用銅導線來打線，其他導線也可使用，例如金或鋁。此外，儘管本發明已經使用球焊進行，但是其不限於球焊，而且可以楔焊(wedge bonding)實 行。
儘管本發明原則上已經連結清潔半導體基材描述過，但是本發明的清潔組合物可用以清潔包括有機及無機殘餘物的任何基材。
實施例
以下實施例舉例說明清潔溶液A1、A2、B1及B2能除去該等焊墊上的金屬氧化物及接點。這些清潔溶液也能除去污染物、氟化物及該等焊墊及接點上的其他殘餘物。這些清潔溶液將會使該等金屬表面成為更乾淨的狀態，所以該等金屬導線在打線時將具有良好黏附力。清潔溶液A1及A2，其相當於以上的組合物A，將從鋁焊墊移除金屬氧化物。清潔溶液B1及B2，其相當於以上的組合物B，將從銅焊墊移除金屬氧化物。所估測的組合物如以下：
清潔溶液A1：二甲基乙醯胺(57.5%)；去離子水(13.9%)；醋酸銨(15.6%)；醋酸(12.0%)；氟化銨(1.0%)。
清潔溶液A2：N-甲基-2-吡咯烷酮(63.9%)；去離子水(30.0%)；醋酸銨(2.6%)；醋酸(2.0%)；氟化銨(0.50%)；羧基苯并三唑(1.0%)。
清潔溶液B1：去離子水(98.333%)；檸檬酸(0.667%)；丙二酸(0.333%)；草酸(0.667%)。
清潔溶液B2：去離子水(98.27%)；檸檬酸(0.667%)；丙二酸(0.333%)；草酸(0.667%)；SAS-10(0.063%)。
於清潔溶液A1、A2、B1及B2中清潔引線架(其具有 附接的晶粒)的方法如以下。在該晶粒附接固化步驟之後及該打線步驟之前把該等清潔溶液施於該等引線架。依以下任一方式把該等清潔溶液施於該等引線架：1)將該等引線架沉浸於該清潔溶液槽中，2)將該清潔溶液噴灑於該等引線架上。該等清潔溶液的最佳溫度介於25℃至50℃。暴露於該等清潔溶液的最佳時間介於5分鐘至30分鐘。等暴露於該等清潔溶液之後，以去離子水沖洗該等引線架。該去離子水沖洗的最佳溫度是25℃(室溫)。該去離子水沖洗的最佳時間介於30秒至3分鐘。等到在去離子水中沖洗該等引線架之後將其乾燥。一旦該等引線架均已經乾燥，其可前往該打線步驟。
組合物A除去氧化鋁的能力
以下顯示的是使用X-射線光電子光譜儀(XPS)收集到的數據。此數據係於一完整晶圓上的晶粒上的鋁焊墊上收到集。在暴露於清潔溶液A之前。該鋁焊墊上的氧化鋁層厚度是約70至85 Å。等暴露於清潔溶液A1及A2之後該氧化鋁厚度減至約30至40 Å，其係自然形成於鋁表面上的天然氧化物層的典型厚度。此數據表示清潔溶液A1及A2除去該氧化鋁而且接著氧化鋁的天然層再長回來。暴露於清潔溶液A1及A2之後的氧化鋁厚度淨減量大並且會改善打線時該等金屬導線與該等鋁焊墊之間的黏附力。
處理條件：清潔溶液→去離子水，25℃，30秒→N2 吹乾
參照圖3，呈現另一個顯示清潔溶液A1除去氧化鋁的數據。此數據使用歐傑縱深分佈(Auger depth profiling)收集到。在暴露於清潔溶液A1之前，氧存於該鋁金屬中一直到約100 Å的深度。因此，這是該氧化鋁層厚度的測量。等暴露於清潔溶液A1之後氧僅滲入該鋁一直到約35 Å的深度。該氧化鋁厚度實質上減小了。而且這是讓暴露的鋁焊墊靜置於空氣中3天以後的情形。也顯示讓該等鋁焊墊靜置於空氣中14天以後的另一數據。同樣地，該氧濃度的滲透深度比暴露於清潔溶液A1之前小非常多。
組合物A除去鋁焊墊上的氟化物的能力
會造成差的黏附力的鋁焊墊上的另一污染物使氟(F)被埋入。氟會來到該鋁焊墊上，舉例來說，在用以蝕刻穿過該鈍化層並且打開該鋁焊墊的電漿蝕刻製程期間。該電漿經常是以CF4 為基礎，所以來自該電漿的氟會來到該鋁表面上。氟會與空氣中的濕氣反應而造成該等鋁焊墊上的 腐蝕。只要氟仍在鋁上此腐蝕將會持續發生。所以除去氟將會使鋁焊墊靜置於空氣中時發生的腐蝕減至最低限度。若是發生較少腐蝕則鋁表面將會更乾淨而且該等金屬導線將會對該等焊墊具有較好的黏附力。圖4及5顯示清潔溶液A1從鋁焊墊除去氟的能力。
保護下面的鋁之組合物A
清潔溶液A1及A2能非常有效除去氧化鋁但是其也必須對下面的鋁金屬具有非常小的蝕刻速率。若是其除去氧化鋁而且嚴重蝕刻下面的鋁金屬，則該打線效能可能沒獲得改善。以下表2的數據顯示清潔溶液A1及A2對於鋁具有非常低的蝕刻速率。
組合物B除去氧化銅及使再生長速率最小化的能力
使用橢圓光度法收集圖6及7舉例說明的數據。在暴露於該等清潔溶液之前測量在銅空白晶圓上的氧化銅初始厚度。該數據顯示此氧化銅初始厚度(圖形中顯示於時間=-1日)是約25至30 Å厚。等到暴露於清潔溶液B1及B2 之後氧化銅的厚度降至約5至10 Å。此數據表示清潔溶液B1及B2已除去大部分的氧化銅。銅會自然鈍化並且形成天然氧化物層。每隔數日再測量氧化銅層的厚度一直到14日。在這14日的期間使該銅晶圓暴露於周遭的空氣。數據顯示經過14日氧化銅再生長緩慢。所以清潔溶液B1及B2不僅除去氧化銅，其亦將氧化銅的再生長速率減至最低限度。
組合物B保護下面的銅
清潔溶液B1及B2能非常有效除去氧化銅但是其也必須對下面的銅金屬具有非常小的蝕刻速率。若是其除去氧化銅而且嚴重蝕刻下面的銅金屬，則該打線效能可能沒獲得改善。以下表3的數據顯示清潔溶液B1及B2對於銅具有非常低的蝕刻速率。
清潔溶液A的其他實施例
使用帶有攪拌棒的燒杯進行以下實驗以模擬該引線架清潔製程。
清潔溶液A1(以上揭示的)係製備如下：對1公升的HDPE聚合物瓶(poly-bottle)添加575 gm的二甲基乙醯胺(DMAc)、139 gm的去離子水(DIW)、156 gm的醋酸銨、120 gm的醋酸及10 gm的氟化銨。蓋上該瓶子並且加以搖晃。以去離子水稀釋清潔溶液A1的試樣以製造一5%溶液而且測得該溶液的pH為4.9。
此實驗中測試的鋁或Al2 O3 晶圓為空白晶圓。把晶圓沉浸於該燒杯中調定於持續90分鐘。
具有338.24 ohms-Å/Sq的電阻率之氮化鈦(TiN)基材上鋁(0.5%銅)金屬係自SVMI獲得並且具有標稱厚度8000Å的鋁。儲存時該鋁基材會長到至多150Å的氧化物層。在蝕刻速率測定之前該鋁基材因此藉由於25℃將2”x2”的鋁片沉澱於去離子水中含42.5重量% H3 PO4 的水溶液中2分鐘預處理好。經過沉澱2分鐘之後，以去離子水沖洗該鋁片3分鐘，以N2 槍乾燥30秒，並且接著測量鋁膜厚度。依此方式預處理好的鋁片立即用於進行蝕刻速率測量。
鋁或Al2 O3 除去試驗係進行如下。把各自2”x2”的片子之鋁或Al2 O3 基材沉浸於在500 ml玻璃燒杯中的330 ml的清潔溶液A1並且在處於300 rpm的磁攪拌板(stir plate)上攪拌該溶液。溫度記錄為25℃。在時間0、20、40、60及90分鐘之後進行以Å表示的厚度度量3次。
使用ResMap四點探針完成鋁厚度度量。接著做該膜厚度對比於時間數據的迴歸。關於清潔溶液A1測得對於鋁 的蝕刻速率為1.8 Å/min。
進行橢圓光度法試驗以使用FilmTek SCI橢圓儀測量該Al2 O3 氧化物厚度。接著做膜厚度對比於時間數據的迴歸。關於清潔溶液A1測得對於Al2 O3 的蝕刻速率為10.1 Å/min。
如同A1般製備其他清潔溶液A94B、A94E、A97E、A97F及A97G但是變化組分的濃度。在這些溶液中去離子水負責該組合物的其餘部分以調製成100重量%。表I中彙總這些溶液組成、其pH度量及其蝕刻速率結果。關於鋁及Al2 O3 的蝕刻速率顯示變化鋁及Al2 O3 的相對蝕刻速率可藉由變化組分濃度獲得。該鋁溶液顯示Al2 O3 蝕刻速率比鋁蝕刻速率高。
如同清潔溶液A1般製備清潔溶液A96G但是利用丙二醇(PG)替代DMAC。表II中彙總組成、其pH度量及蝕刻速率結果並且與清潔溶液A1做比較。
如同清潔溶液A1般製備清潔溶液A94A、A94D、A96A及A96B但是利用PG替代DMAC。在這些溶液中去離子水負責該組合物的其餘部分以調製成100重量%。表III中彙總組成、其pH度量及蝕刻速率結果。該等實施例顯示鋁及Al2 O3 的相對蝕刻速率可藉由變更組分及緩衝劑濃度以達成預期的清潔效能。
如同清潔溶液A1般製備清潔溶液A96E及A96F但是利用PG替代DMAC。在這些溶液中去離子水負責該組合物的其餘部分以調製成100重量%。表IV中彙總組成、其pH度量及蝕刻速率結果並且與A96A及A97E做比較。因為於較低溶劑濃度的水性配方有時候可能較佳，所以使用較少量溶劑。由溶劑對水的相對量、氟化物量及溶液pH給予特定應用最好的清潔。溶劑類型能進一步微調清潔結果。
如同清潔溶液A1般製備清潔溶液A96C、A96D、A97B及A97D但是利用二甲基脲(DMU)溶劑，並且顯示將二丙二醇單甲醚(DPM)共溶劑加於PG的效應。在這些溶液中去離子水負責該組合物的其餘部分以調製成100重量%。表V中彙總組成、其pH度量及蝕刻速率結果並且與A96A及A96B做比較。
清潔溶液B的其他實施例
如同清潔溶液A1般製備清潔溶液B91A、B92A、B92D、B92E及B92F但是使用表VI所示的組分源始。在這些溶液中去離子水負責該組合物的其餘部分以調製成100重量%。使用0.45重量%檸檬酸及0.0017重量% NH4 F加水基質，測定關於0、10、30及40重量% PG配方的蝕刻速率。
如同清潔溶液A1般製備清潔溶液B92F、B92H、B92I及B92J但是使用表VII所示的組分源始。在這些溶液中去離子水負責該組合物的其餘部分以調製成100重量%。
關於B100A、B100B、B100C、B100D及B101A中的B1清潔溶液使用其他腐蝕抑制劑分子進行其他試驗。檸檬酸是0.45重量%絕對量。
前述實施例及較佳具體實施例的敘述，理應視為舉例說明，而非限制由申請專利範圍來界定的發明。非常容易明白的是，以上所述的組合物中的特徵及組分的眾多變化 及組合均可加以利用而不會悖離申請專利範圍所述的發明。這樣的變化不得視為本發明的精神及範疇的悖離，而且意欲將所有這樣的變化包括在下列申請專利範圍的範疇之內。再者儘管沒以多重附屬形式書寫，但是本發明揭示並且包括所有具體實施例作為其揭示內容的一部分，猶如所有附屬申請專利範圍均為附屬於前述申請專利範圍任一項的多重附屬申請專利範圍。此外文中所述的所有組分均可依任何的範圍組合結合。所有包含的語法包括基本上由...組成及由...組成。
前述的發明內容以及本發明的較佳具體實施例的詳細描述，聯合附加圖形閱讀時將更易於理解。為了達到舉例說明本發明的目的，在該等圖形中顯示目前較佳的具體實施例。然而，理應瞭解的是本發明不限於所示的精確配置及工具。在該等圖形中：圖1是舉例說明在製備積體電路時涉及的習知步驟的方塊圖；圖2是舉例說明本發明方法的步驟之方塊圖；圖3是舉例說明本發明之一具體實施例的鋁表面處理效能的圖形；圖4是舉例說明本發明之一具體實施例的效能的圖形；圖5是舉例說明本發明之一具體實施例的效能的圖 形；圖6是本發明之一具體實施例從氧化銅移除及再生長的觀點來看效能的圖形；及圖7是本發明之一具體實施例從氧化銅移除及再生長的觀點來看效能的圖形。

Claims (22)

  1. 一種處理引線架組合件之方法，以從該引線架組合件除去不欲的材料或預備該引線架組合件表面以供隨後打線用，其中該引線架組合件包含一或更多下列零件：引線架、晶粒、有焊墊在上面的晶粒、接點、接點引線及導線，該方法包含下列步驟：將上述一或更多晶粒附接於上述引線架，上述引線架包含具有暴露的金屬表面之上述接點引線；及使該引線架組合件的至少一部分或該引線架組合件的一或更多零件與包含水和至少一酸或至少一鹽的組合物接觸。
  2. 如申請專利範圍第1項之方法，其中上述方法另外包含下列步驟：乾燥該引線架組合件或該引線架組合件的一或更多零件；及進行打線步驟，其包含將導線附接於該晶粒上的焊墊與該引線架上的接點引線之間。
  3. 如申請專利範圍第1項之方法，其另外包含在該引線架組合件上面形成塑模以形成一封裝電路的步驟。
  4. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物具有約1至約7的pH。
  5. 如申請專利範圍第1項之方法，其另外包含經過該接觸步驟之後，該引線架組合件或該引線架組合件的一或更多零件的乾燥步驟，其中上述接觸步驟所用的上述組合物包含酸緩衝液，上述酸緩衝液包含按照介於10：1至1：10的酸對鹽莫耳比之選自由羧酸及多元酸所組成的群組之酸及該酸之鹽。
  6. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物另外包含選自由有機極性溶劑、氟化物、界面活性劑及腐蝕抑制劑所組成的群組之一或更多組分。
  7. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物另外包含有機極性溶劑及氟化物。
  8. 如申請專利範圍第5項之方法，其另外包含下列步驟：在上述乾燥步驟之後進行打線步驟，該打線步驟包含將導線附接於該晶粒上的焊墊與該引線架上的接點引線之間；其中上述接觸步驟所用的上述組合物中的上述酸緩衝液包含至少一選自由以下所組成的群組者：醋酸/醋酸鹽類、苯甲酸/苯甲酸鹽類及酚酸/酚酸鹽類。
  9. 如申請專利範圍第1項之方法，其中上述組合物另外包含選自由二甲基乙醯胺(DMAC)、單乙醇胺、N-甲基乙醇胺、甲醯胺、N-甲基甲醯胺、γ-丁內酯、N-甲基吡咯烷酮、二羥醇類、多羥醇類、二醇類及多元醇類例如(C2 -C20 )烷二醇類及(C3 -C20 )烷三醇類、環狀醇類及經取代的醇類及甘醇類、二醇醚、四氫呋喃甲醇(THFA)、二丙酮醇、丙二醇、1,4-環己二甲醇及尿素類及其混合物所組成的群組之溶劑。
  10. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物包含約0.003至約4重量%的至少一選自由以下所組成的群組者：羥基羧酸、該羥基羧酸的鹽、該羥基羧酸和該羥基羧酸鹽的混合物、含胺基的羧酸、該含胺基的羧酸的鹽、該含胺基的羧酸和該含胺基的羧酸鹽的混合物，及其混合物。
  11. 如申請專利範圍第1項之方法，其另外包含在該接觸步驟之後乾燥該引線架組合件或該引線架組合件的一或更多零件的步驟，其中上述接觸步驟所用的上述組合物具有介於3至7的pH；上述組合物另外包含30重量%至90重量%的有機極性溶劑；0.001重量%至20重量%的氟化物；及至多15重量%的任意界面活性劑，其中上述水存有0.5重量%至40重量%。
  12. 如申請專利範圍第1項之方法，其中氟化物係以0.001重量%至20重量%存於該組合物中，該氟化物係選自由通式R1 R2 R3 R4 NF的化合物所組成的群組，其中R1 、R2 、R3 及R4 係獨立地為氫、醇基、烷氧基、烷基或其混合物。
  13. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物另外包含30重量%至90重量%的有機極性溶劑；0.0005重量%至20重量%的氟化物；0.5重量%至40重量%水；至多15重量%的的任意腐蝕抑制劑或界面活性劑。
  14. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的組合物包含：約0.005至約16重量%的至少一羧酸、其鹽或其混合物；約0.003至約4重量%的至少一選自由以下所組成的群組者：羥基羧酸、該羥基羧酸的鹽、該羥基羧酸和該羥基羧酸鹽的混合物、含胺基的酸、該含胺基的酸的鹽、該含胺基的酸和該含胺基的酸鹽的混合物，及其混合物；及剩餘部分實質上為水。
  15. 如申請專利範圍第1項之方法，其中該方法另外包含下列步驟：在上述接觸步驟之前把個別晶粒附接於包含接點引線 的引線架以形成具有暴露的鋁金屬表面的基材；其中上述接觸步驟所用的上述組合物包含0.003至約25重量%的一或更多羧酸類。
  16. 如申請專利範圍第1項之方法，其中該方法另外包含在上述接觸步驟之後乾燥該引線架組合件或該引線架組合件的一或更多零件的步驟，其中該接觸步驟所用的上述組合物包含一或更多選自由檸檬酸、草酸、丙二酸、丁二酸、胺基戊二酸、己二酸、順丁烯二酸及反丁烯二酸；其鹽類或其混合物所組成的群組的羧酸類。
  17. 如申請專利範圍第1項之方法，其中該方法另外包含在上述接觸步驟之後乾燥該引線架組合件或該引線架組合件的一或更多零件的步驟，其中該接觸步驟所用的上述組合物包含二或更多選自由檸檬酸、草酸、丙二酸、丁二酸、胺基戊二酸、己二酸、順丁烯二酸及反丁烯二酸；其鹽類或其混合物所組成的群組的羧酸類；而且另外包含一或更多溶劑、一或更多氟化物及任意一或更多界面活性劑。
  18. 如申請專利範圍第1項之方法，其中該方法另外包含在上述接觸步驟之後在該引線架組合件上面形成塑模以形成一封裝電路的步驟，而且該接觸步驟所用的上述組合物包含檸檬酸。
  19. 如申請專利範圍第1項之方法，其中該接觸步驟所用的上述組合物另外包含一或更多界面活性劑。
  20. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物包含：約0.1至約3重量%的至少一二羧酸、其鹽或其混合物；約0.05至約1.5重量%的至少一羥基羧酸、其鹽或其混合物；及剩餘部分實質上為水，而且上述組合物具有約1至約4的pH。
  21. 如申請專利範圍第1項之方法，其中上述接觸步驟所用的上述組合物包含：約0.003至約25重量%的一或更多酸類。
  22. 一種用於清潔引線架組合件或引線架組合件的零件之組合物，該組合物係前述方法申請專利範圍項中任一項的接觸步驟所使用者。
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