TWI769770B - 接著性聚合物之分解洗淨組成物,及接著性聚合物之洗淨方法 - Google Patents
接著性聚合物之分解洗淨組成物,及接著性聚合物之洗淨方法 Download PDFInfo
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- TWI769770B TWI769770B TW110112093A TW110112093A TWI769770B TW I769770 B TWI769770 B TW I769770B TW 110112093 A TW110112093 A TW 110112093A TW 110112093 A TW110112093 A TW 110112093A TW I769770 B TWI769770 B TW I769770B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/28—Organic compounds containing halogen
- C11D7/30—Halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明提供蝕刻速度之經時降低受抑制之組成物。該組成物包含四級氟化烷基銨及四級氟化烷基銨之水合物之至少1種、作為非質子性溶劑之(A)於氮原子上不具有活性氫之N-取代醯胺化合物、(B)二丙二醇二甲醚、及抗氧化劑。
Description
本發明有關組成物,及接著性聚合物之洗淨方法。本發明之一實施態樣係有關於半導體晶圓之薄型化製程中,可用以將殘留於裝置晶圓上之使裝置晶圓與支撐晶圓(載體晶圓)暫時接著所使用之包含接著性聚合物之接著劑分解洗淨之組成物、及使用該組成物之接著性聚合物之洗淨方法。
於用以使半導體高密度化之三次元安裝技術中,將半導體晶圓之每1片之厚度變薄,將藉由矽貫通電極(TSV)線連結之複數半導體晶圓積層而成。具體而言,將形成有半導體裝置之裝置晶圓的未形成裝置之面(背面)藉由研磨而薄型化後,於該背面進行包含TSV之電極形成。
裝置晶圓之背面之研磨步驟中,為了對裝置晶圓賦予機械強度,而使用接著劑將亦稱為載體晶圓之支撐晶圓暫時接著於裝置晶圓之半導體裝置形成面。作為支撐晶圓係使用例如玻璃晶圓或矽晶圓。研磨步驟後,根據需要於裝置晶圓之研磨面(背面)形成包含Al、Cu、Ni、Au
等之金屬配線或電極墊、氧化膜、氮化膜等之無機膜或包含聚醯亞胺等之樹脂層。隨後,將裝置晶圓之背面藉由貼合於以環框予以固定之具有丙烯酸黏著層之膠帶,而以膠帶固定裝置晶圓。隨後,將裝置晶圓與支撐晶圓分離(解黏合),剝離裝置晶圓上之接著劑,使用洗淨劑將裝置晶圓上之接著劑殘留物洗淨去除。
於裝置晶圓之暫時接著用途中,使用包含耐熱性良好之聚有機矽氧烷化合物作為接著性聚合物之接著劑。尤其,接著劑為經交聯之聚有機矽氧烷化合物時,對洗淨劑要求切斷Si-O鍵及利用溶劑溶解分解生成物之2種作用。作為此等洗淨劑舉例為例如將氟化四丁基銨(TBAF)等之氟系化合物溶解於極性非質子性溶劑者。由於TBAF之氟化物離子參與經由Si-F鍵結生成之Si-O鍵之切斷,故可對洗淨劑賦予蝕刻性能。極性非質子性溶劑可溶解TBAF,且由於對於氟化物離子不形成經由氫鍵之溶劑合,故可提高氟化物離子之反應性。
專利文獻1(日本特開2014-133855號公報)中記載於極性非質子性溶劑中溶解氫氧化四烷基銨之矽氧烷樹脂之洗淨液。
專利文獻2(日本特表2015-505886號公報)中記載於酯或酮中溶解TBAF之聚矽氧烷之洗淨液。
專利文獻3(日本特開2004-000969號公報)中記載於丙二醇烷基醚醇化物中溶解TBAF之洗淨液。
[專利文獻1]日本特開2014-133855號公報
[專利文獻2]日本特表2015-505886號公報
[專利文獻3]日本特開2004-000969號公報
[發明欲解決之課題]
包含TBAF等之氟化合物及溶劑之洗淨劑中溶劑的角色,作為使反應性物質的極性高的氟化合物充分溶解,與極性低的接著劑之表面的親和性充分者,認為在於確保氟化合物所含之氟化物離子之反應性同時溶解接著劑之分解生成物。
接著劑中所含之接著性聚合物有基於改善耐熱性、剝離性等之目的而導入取代基之情況,藉此有接著劑表面顯示各種極性之情況。期望洗淨劑對於顯示此等各種極性之接著劑表面顯示優異親和性,藉此達成高的蝕刻速度。
本發明人等發現即使欲確保氟化合物所含之氟化物離子之反應性並且溶解接著劑之分解生成物而使用非質子性之N-取代醯胺化合物及二丙二醇二甲醚作為溶劑時,於組成物調製後,伴隨保存期間之經過,仍會產生組成物之蝕刻速度降低之情況。
本發明提供蝕刻速度之經時降低受抑制之組成物。
[用以解決課題之手段]
本發明人等發現藉由使用包含四級氟化烷基銨或其水合物、於氮原子上不具有活性氫之N-取代醯胺化合物、二丙二醇二甲醚及抗氧化劑之組成物,可抑制蝕刻速度之經時降低。
亦即本發明包含如下之[1]~[11]。
[1]
一種組成物,其包含四級氟化烷基銨及四級氟化烷基銨之水合物之至少1種、作為非質子性溶劑之(A)於氮原子上不具有活性氫之N-取代醯胺化合物及(B)二丙二醇二甲醚,及抗氧化劑。
[2]
如[1]之組成物,其中前述抗氧化劑包含選自由二丁基羥基甲苯(BHT)、丁基羥基苯甲醚(BHA)及抗壞血酸所成之群中之至少1種。
[3]
如[1]或[2]之組成物,其中前述抗氧化劑之含量為10質量ppm~ 1000質量ppm。
[4]
如[1]~[3]中任一項之組成物,其中前述(A)N-取代醯胺化合物係以式(1)表示之2-吡咯啶酮衍生化合物:
(式(1)中,R1
表示碳原子數1~4之烷基)。
[5]
如[4]之組成物,其中前述(A)N-取代醯胺化合物係式(1)中R1
為甲基或乙基之2-吡咯啶酮衍生化合物。
[6]
如[1]~[5]中任一項之組成物,其中前述四級氟化烷基銨之含量為0.01~10質量%。
[7]
如[1]~[6]中任一項之組成物,其中前述四級氟化烷基銨係以式(2)表示之氟化四烷基銨:
(式(2)中,R2
~R5
分別獨立表示選自由甲基、乙基、正丙基、異丙基及正丁基所成之群中之烷基)。
[8]
如[1]~[7]中任一項之組成物,其中相對於前述非質子性溶劑100質量%,前述(A)N-取代醯胺化合物之含量為50~95質量%,前述(B)二丙二醇二甲醚之含量為5~50質量%。
[9]
如[1]~[8]中任一項之組成物,其係接著性聚合物之分解洗淨組成物。
[10]
如[9]之組成物,其中前述接著性聚合物係聚有機矽氧烷化合物。
[11]
一種洗淨方法,係使用如[1]~[10]中任一項之組成物洗淨基材上之接著性聚合物。
[發明效果]
本發明之組成物可抑制蝕刻速度之經時降低。如此有利於組成物之長期保管。
上述記載不能視為揭示本發明之全部實施態樣及本發明有關之所有優點者。
以下顯示例示之實施形態更詳細說明本發明。
[組成物]
一實施態樣之組成物包含四級氟化烷基銨及四級氟化烷基銨之水合物之至少1種、作為非質子性溶劑之(A)於氮原子上不具有活性氫之N-取代醯胺化合物及(B)二丙二醇二甲醚(DPGDME),及抗氧化劑。
一實施態樣之組成物含有作為溶劑之於氮原子上不具有活性氫(氫原子未直接鍵結於氮原子)之N-取代醯胺化合物(亦簡稱為「N-取代醯胺化合物」)。已知N-取代醯胺化合物藉由與氧接觸而緩緩氧化而生成氧化物。例如N-甲基吡咯啶酮(NMP)經氧化時,生成以N-甲基丁二醯亞胺為代表之NMP衍生物。該N-取代醯胺化合物之氧化生成物由於產生具有對於組成物中之氟化物離子具有活性之氫原子之生成物,故使氟化物離子之活性降低,其結果認為使蝕刻速度經時降低。因此,為了維持蝕刻速度,認為期望抑制N-取代醯胺化合物之氧化。
<四級氟化烷基銨及其水合物>
四級氟化烷基銨及其水合物釋出參與Si-O鍵之切斷的氟化物離子。四級烷基銨部分可使鹽的四級氟化烷基銨溶解於非質子性溶劑。作為四級氟化烷基銨可無特別限制地使用各種化合物。作為四級氟化烷基銨之水合物舉例為例如三水合物、四水合物及五水合物。四級氟化烷基銨可為1種或2種以上之組合。四級氟化烷基銨之非水合物與水合物可以任意比例使用。
一實施態樣中,四級氟化烷基銨係以式(2)表示之氟化四烷基銨:
(式(2)中,R2
~R5
分別獨立表示選自由甲基、乙基、正丙基、異丙基及正丁基所成之群中之烷基)。基於取得容易性之觀點,較佳R2
~R5
全部為相同的烷基。作為此等四級氟化烷基銨舉例為氟化四甲基銨、氟化四乙基銨、氟化四丙基銨、氟化四丁基銨等。基於分解洗淨性能、取得容易性、價格等之觀點,四級氟化烷基銨較佳為氟化四丁基銨(TBAF)。
組成物中之四級氟化烷基銨之含量較佳為0.01~10質量%。此處「四級氟化烷基銨之含量」於組成物中包含四級氟化烷基銨之水合物時,係水合物水的質量除外,作為僅四級氟化烷基銨之質量而換算之值。組成物中之四級氟化烷基銨之含量更佳為1~10質量%,又更佳為3~7質量%,特佳為4~6質量%。藉由使四級氟化烷基銨之含量為0.01質量%以上,可有效分解及洗淨接著性聚合物,藉由為10質量%以下,可防止或抑制裝置晶圓之裝置形成面所含之金屬部分的腐蝕。
<非質子性溶劑>
組成物包含(A)於氮原子上不具有活性氫之N-取代醯胺化合物及(B)二丙二醇二甲醚作為非質子性溶劑。
組成物中之非質子性溶劑之含量較佳為80~99.98質量%,更佳為85~99.95質量%,又更佳為90~99.9質量%。
[(A)於氮原子上不具有活性氫之N-取代醯胺化合物]
(A)於氮原子上不具有活性氫之N-取代醯胺化合物(亦簡稱為「(A)N-取代醯胺化合物」)係比較高極性的非質子性溶劑,可均一溶解或分散組成物中之四級氟化烷基銨及其水合物。一實施態樣中,「(A)N-取代醯胺化合物」亦包含於氮原子上不具有活性氫之尿素化合物(carbamide化合物)。作為(A)N-取代醯胺化合物可無特別限定地使用各種化合物,舉例為例如N,N-二甲基甲醯胺(DMF)、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N,N-二甲基丙醯胺、N,N-二乙基丙醯胺、四甲基尿素等之非環式N-取代醯胺;2-吡咯啶酮衍生物、2-哌啶酮衍生物、ε-己內醯胺衍生物、1,3-二甲基-2-咪唑啶酮(DMI)、1-甲基-3-乙基-2-咪唑啶酮、1,3-二乙基-2-咪唑啶酮、1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮(N,N’-二甲基伸丙基尿素)等之環式N-取代醯胺。該等中,(A)N-取代醯胺化合物較佳為環式N-取代醯胺。(A)N-取代醯胺化合物可為1種或2種以上之組合。
一實施態樣中,(A)N-取代醯胺化合物係以式(1)表示之2-吡咯啶酮衍生化合物。
(式(1)中,R1
表示碳原子數1~4之烷基)。作為碳原子數1~4之烷基舉例為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等。作為以式(1)表示之2-吡咯啶酮衍生化合物舉例為例如N-甲基吡咯啶酮(NMP)、N-乙基吡咯啶酮(NEP)、N-丙基吡咯啶酮、N-丁基吡咯啶酮等。
基於極性比較高,四級氟化烷基銨之溶解能力優異、取得容易,(A)N-取代醯胺化合物較佳為式(1)中R1
為甲基或乙基之2-吡咯啶酮衍生化合物,更佳為式(1)中R1
為甲基之2-吡咯啶酮衍生化合物,亦即N-甲基吡咯啶酮。
非質子性溶劑中之N-取代醯胺化合物含量,相對於前述非質子性溶劑100質量%,較佳為50~95質量%,更佳為60~95質量%,又更佳為70~90質量%。
[(B)二丙二醇二甲醚]
(B)二丙二醇二甲醚(DPGDME)藉由與(A)N-取代醯胺化合物組合,可形成對於接著劑表面顯示高親和性之混合溶劑系。使用此等混合溶劑系之組成物,可達成有效利用了四級氟化烷基銨之反應活性的高蝕刻速度。
非質子性溶劑中之二丙二醇二甲醚含量,於將非質子性溶劑設為100質量%時,較佳為5~50質量%,更佳為5~40質量%,又更佳為10 ~30質量%。
[追加的非質子性溶劑]
組成物亦可包含(A)N-取代醯胺化合物及(B)二丙二醇二甲醚以外之追加的非質子性溶劑。作為此等追加的非質子性溶劑舉例為例如乙二醇二甲醚、丙二醇二甲醚、二乙二醇二甲醚、三丙二醇二甲醚、三丙二醇二乙醚、三丙二醇二正丁醚、四乙二醇二甲醚、四丙二醇二甲醚等之二醇的二烷醚;二丁醚、二戊醚、二己醚、二庚醚、二辛醚、丁基己基醚、丁基辛基醚等之二烷醚等。
追加的非質子性溶劑之引火點較佳為21℃以上。藉由使用引火點為21℃以上,亦即非屬於危險物第4類第1石油類之追加的非質子性溶劑,可減輕組成物之製造及使用中之設備、作業環境等之要件。例如二乙二醇二甲醚及二丁醚之引火點分別為51℃及25℃。又,二丙二醇二甲醚之引火點為60℃。引火點係藉由封籤密閉法(JIS K 2265-1:2007)測定。
非質子性溶劑中之追加的非質子性溶劑含量,於將非質子性溶劑設為100質量%時,較佳為10質量%以下,更佳為5質量%以下,又更佳為1質量%以下。一實施態樣中,非質子性溶劑不含追加的非質子性溶劑,亦即係由(A)N-取代醯胺化合物及(B)二丙二醇二甲醚而成。
<抗氧化劑>
抗氧化劑防止溶劑中之N-取代醯胺化合物被空氣氧化生成氧化物。抗氧化劑種類並未特別限定,但舉例為例如二丁基羥基甲苯(BHT)、丁基羥基苯甲醚(BHA)、抗壞血酸及其衍生物、生育酚及其衍生物、異抗壞血酸鈉等。該等抗氧化劑對於非質子性溶劑之溶解性優異,亦可作為(B)二丙二醇二甲醚及其他醚的抗氧化劑而作用。抗氧化劑可僅使用1種,亦可組合2種以上使用。基於取得容易性、價格等之觀點,抗氧化劑較佳為選自由二丁基羥基甲苯(BHT)、丁基羥基苯甲醚(BHA)及抗壞血酸所成之群之至少1種,更佳為二丁基羥基甲苯(BHT)。
組成物中之抗氧化劑含量較佳為10質量ppm~1000質量ppm。組成物中之抗氧化劑含量更佳為10質量ppm~500質量ppm,又更佳為20質量ppm~200質量ppm,特佳為30質量ppm~100質量ppm。藉由使抗氧化劑之含量為上述範圍,可更有效抑制蝕刻速度之經時降低。且,藉由使抗氧化劑含量為1000質量ppm以下,可保持與未使用抗氧化劑時同等的初期蝕刻速度,且可抑制組成物起因於抗氧化劑或其反應生成物之著色。
<添加劑及其他成分>
在不顯著損及本發明效果之範圍,組成物可包含界面活性劑、防腐劑、發泡防止劑等之添加劑作為任意成分。
一實施態樣中,組成物實質上不含或不含質子性溶劑。例如組成物中之質子性溶劑含量為5質量%以下、3質量%以下或1質量%以下。組成物中所含之質子性溶劑可為源自四級氟化烷基銨之水合物的水。
一實施態樣中,組成物實質上不含或不含選自酮及酯之非質子性溶劑。例如組成物中選自酮及酯之非質子性溶劑含量為1質量%以下、0.5質量%以下或0.1質量%以下。該實施態樣中,於氟化合物存在下,抑制了因自酮或酯生成之反應生成物(羥醛反應自我縮合物)或分解生成物(醇及羧酸)溶劑合於氟化物離子所致之氟化物離子之失活,可抑制蝕刻速度之經時降低。
一實施態樣之組成物可作為各種接著劑所含之接著性聚合物之分解洗淨組成物使用。接著性聚合物若為可使用一實施形態之組成物洗淨者則未特別限定。接著劑除了接著性聚合物以外,亦可包含硬化劑、硬化促進劑、交聯劑、界面活性劑、調平劑、填充材等作為任意成分。
<接著性聚合物>
一實施形態中,接著性聚合物包含Si-O鍵。接著性聚合物藉由四級氟化烷基銨之氟化物離子切斷Si-O鍵而低分子化或喪失交聯構造,成為可溶解於非質子溶劑中,其結果,可自裝置晶圓等之表面去除接著性聚合物。
包含Si-O鍵之接著性聚合物較佳為聚有機矽氧烷化合物。由於聚有機矽氧烷化合物包含多數矽氧烷鍵(Si-O-Si),故使用組成物可有效分解及洗淨。作為聚有機矽氧烷化合物舉例為例如矽氧彈性體、矽氧凝膠及MQ樹脂等之矽氧樹脂以及該等之環氧改質體、丙烯酸改質體、甲基丙烯酸改質體、胺基改質體、巰基改質體等之改質體。聚有機矽氧烷化合物可為矽氧改質聚胺基甲酸酯、矽氧改質丙烯酸樹脂等之矽氧改質聚合物。
一實施態樣中,接著性聚合物可為加成硬化型矽氧彈性體、矽氧凝膠或矽氧樹脂。該等加成硬化型矽氧包含含乙烯性不飽和基之聚有機矽氧烷例如乙烯基末端聚二甲基矽氧烷或乙烯基末端MQ樹脂與作為交聯劑之聚有機氫矽氧烷例如聚甲基氫矽氧烷,使用鉑觸媒等之氫矽烷化觸媒予以硬化。
其他實施態樣中,接著性聚合物包含含有芳烷基、環氧基或苯基之聚二有機矽氧烷,特別是包含含芳烷基、環氧基或苯基之聚二甲基矽氧烷。包含此等接著性聚合物之接著劑亦可與包含上述加成硬化型矽氧之接著劑組合使用於暫時接著。
[接著性聚合物之洗淨方法]
位於矽晶圓等之基材上之接著性聚合物之洗淨可使用組成物,藉以往習知之各種方法進行。作為接著性聚合物之洗淨方法舉例為例如使用旋轉塗佈機以特定速度使基材旋轉,同時於基材上噴出組成物(旋轉蝕刻)以與接著性聚合物接觸、對於基材上之接著性聚合物噴霧組成物(噴霧)、將具有接著性聚合物之基材浸漬於放入組成物之槽中(浸漬)等。分解洗淨的溫度根據基材上之接著性聚合物之種類及附著量而有各種,一般為20℃~90℃,較佳為40℃~60℃。分解洗淨的時間根據基材上之接著性聚合物之種類及附著量而有各種,一般為5秒~10小時,較佳為10秒~2小時。分解洗淨時,亦可對組成物之浴或基材適用超音波。
分解洗淨後,亦可使用異丙醇(IPA)等之醇、離子交換水(DIW)等清洗基材,亦可藉由吹拂氮氣、空氣等、於常壓下或減壓下加熱等將基材乾燥。
[裝置晶圓之製造方法]
一實施形態中,裝置晶圓之製造方法包含使用組成物洗淨裝置晶圓上之接著性聚合物。洗淨後,根據需要亦可將裝置晶圓清洗或乾燥。
裝置晶圓之製造方法進而包含以下步驟:於矽晶圓等之基材上形成半導體裝置獲得裝置晶圓,使裝置晶圓之半導體裝置形成面與支撐晶圓對向,將裝置晶圓與支撐晶圓藉由包含接著性聚合物之接著劑暫時接著,藉由研磨裝置晶圓之裝置形成面之相反面(背面)而使裝置晶圓薄型化,自裝置晶圓分離支撐晶圓。半導體裝置之形成、裝置晶圓與支撐晶圓之暫時接著、裝置晶圓之背面研磨、及裝置晶圓自支撐晶圓之分離可藉以往習知方法進行,未特別限定。
[支撐晶圓之再生方法]
組成物可使用於裝置晶圓之製造中使用之支撐晶圓的再生。一實施態樣中,支撐晶圓之再生方法包含使用組成物洗淨支撐晶圓上之接著性聚合物。洗淨後,根據需要亦可將支撐晶圓清洗或乾燥。
[實施例]
以下基於實施例更詳細說明本發明,但本發明不受實施例之限制。
[實施例1]
包含抗氧化劑(BHT)之組成物之調製
於125mL之聚乙烯容器中,投入3.332g之氟化四丁基銨・三水合物(TBAF・3H2
O)及0.0030g之二丁基羥基甲苯(BHT)(東京化成工業股份有限公司),依序投入38.934g之N-甲基吡咯啶酮(NMP)、12.017g之二丙二醇二甲醚(DPGDME)(日本乳化劑股份有限公司)並混合,使TBAF・3H2
O溶解。如此,調製包含55質量ppm之BHT的NMP:DPGDME之質量比為0.764:0.236的5質量%TBAF混合溶劑之組成物。又,以同樣順序投入0.0059g或0.0291g之BHT,調製包含BHT 109質量ppm或536質量ppm之NMP:DPGDME之質量比為0.764:0.236之5質量%TBAF混合溶劑之組成物。
[比較例1]
除了實施例1中不使用BHT以外,以同樣順序調製NMP:DPGDME之質量比為0.764:0.236之5質量%TBAF混合溶劑之組成物。
洗淨試驗
將12吋(300mm)矽晶圓(厚770μm)分割為1.5cm×1.5cm之尺寸。將SYLGARD(註冊商標)184(杜邦東麗特用材料股份有限公司製)之主劑2.1484g與硬化劑0.2137g混合成之接著劑以滴管吸出,於經分割之矽晶圓上滴下一滴。隨後,以乾燥機(125℃)加熱20分鐘,於矽晶圓上形成接著劑層。將其作為試驗片,使用測微計測定試驗片中心部之厚度。
於磁攪拌器上放置容積50cc之螺口瓶。於螺口瓶中投入15.0mL之剛調製後(調製後30分鐘以內)之組成物及攪拌子。於組成物中浸漬1片試驗片,於室溫(25℃)以900rpm旋轉數使攪拌子旋轉5分鐘。浸漬後,以鑷子取出試驗片,使用異丙醇(IPA)之洗瓶充分清洗。隨後同樣使用離子交換水(DIW)之洗瓶充分清洗試驗片。對試驗片吹附氮氣使附著的水乾燥後,使用測微計測定試驗片中心部之厚度。將試驗前後之乾燥片的厚度差除以5(min)所得之值作為蝕刻速度(ER)。對調製組成物後第7天、第14天、第25天亦進行同樣試驗。
測定實施例1及比較例1之蝕刻速度的結果示於表1。
[實施例2]
包含抗氧化劑(BHA)之組成物之調製
於125mL之聚乙烯容器中,投入3.332g之氟化四丁基銨・三水合物(TBAF・3H2
O)及0.03054g之丁基羥基苯甲醚(BHA)(關東化學股份有限公司),依序投入38.957g之N-甲基吡咯啶酮(NMP)、12.156g之DPGDME(日本乳化劑股份有限公司)並混合,使TBAF・3H2
O溶解。如此,調製包含560質量ppm之BHA的NMP:DPGDME之質量比為0.764:0.236的5質量%TBAF混合溶劑之組成物。又,以同樣順序投入0.00335g或0.00654g之BHA,調製包含BHA 55質量ppm或108質量ppm之NMP:DPGDME之質量比為0.764:0.236之5質量%TBAF混合溶劑之組成物。
[實施例3]
包含抗氧化劑(抗壞血酸)之組成物之調製
以與實施例2同樣順序,投入L-(+)-抗壞血酸(關東化學股份有限公司)0.02998g,調製包含500質量ppm之L-(+)-抗壞血酸的NMP:DPGDME之質量比為0.764:0.236的5質量%TBAF混合溶劑之組成物。又,以同樣順序投入0.00360g或0.00597g之L-(+)-抗壞血酸,調製包含L-(+)-抗壞血酸57質量ppm或99質量ppm之NMP:DPGDME之質量比為0.764:0.236之5質量%TBAF混合溶劑之組成物。
以與實施例1同樣方法測定實施例2及3之蝕刻速度的結果示於表2。
本發明之組成物可適當地使用於自裝置晶圓上分解洗淨於半導體晶圓之薄型化製程使用之接著劑,尤其是包含聚有機矽氧烷化合物作為接著性聚合物之接著劑的殘留物之用途。
Claims (10)
- 一種接著性聚合物之分解洗淨組成物,其包含四級氟化烷基銨及四級氟化烷基銨之水合物之至少1種、作為非質子性溶劑之(A)於氮原子上不具有活性氫之N-取代醯胺化合物及(B)二丙二醇二甲醚,及抗氧化劑,前述四級氟化烷基銨之含量為0.01~10質量%,前述抗氧化劑之含量為10質量ppm~1000質量ppm,且相對於前述非質子性溶劑100質量%,前述(A)N-取代醯胺化合物之含量為50~95質量%,前述(B)二丙二醇二甲醚之含量為5~50質量%。
- 如請求項1之接著性聚合物之分解洗淨組成物,其中前述抗氧化劑包含選自由二丁基羥基甲苯(BHT)、丁基羥基苯甲醚(BHA)及抗壞血酸所成之群中之至少1種。
- 如請求項1或2之接著性聚合物之分解洗淨組成物,其中前述抗氧化劑之含量為10質量ppm~500質量ppm。
- 如請求項4之接著性聚合物之分解洗淨組成物,其中前述(A)N-取代醯胺化合物係式(1)中R1為甲基或乙基之2-吡咯啶酮衍生化合物。
- 如請求項1或2之接著性聚合物之分解洗淨組成物,其中前述四級氟化烷基銨之含量為1~10質量%。
- 如請求項1或2之接著性聚合物之分解洗淨組成物,其中前述四級氟化烷基銨係以式(2)表示之氟化四烷基銨:R2R3R4R5N+F- (2)(式(2)中,R2~R5分別獨立表示選自由甲基、乙基、正丙基、異丙基及正丁基所成之群中之烷基)。
- 如請求項1或2之接著性聚合物之分解洗淨組成物,其中相對於前述非質子性溶劑100質量%,前述(A)N-取代醯胺化合物之含量為60~95質量%,前述(B)二丙二醇二甲醚之含量為5~40質量%。
- 如請求項1或2之接著性聚合物之分解洗淨組成物,其中前述接著性聚合物係聚有機矽氧烷化合物。
- 一種洗淨方法,係使用如請求項1~9中任一項之接著性聚合物之分解洗淨組成物洗淨基材上之接著性聚合物。
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