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TWI662063B - 感光性聚醯亞胺組成物及其所製成之光阻膜 - Google Patents

感光性聚醯亞胺組成物及其所製成之光阻膜 Download PDF

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TWI662063B
TWI662063B TW107103882A TW107103882A TWI662063B TW I662063 B TWI662063 B TW I662063B TW 107103882 A TW107103882 A TW 107103882A TW 107103882 A TW107103882 A TW 107103882A TW I662063 B TWI662063 B TW I662063B
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楊子瑾
鍾明哲
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新應材股份有限公司
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Priority to CN201810383164.5A priority patent/CN110133963B/zh
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Abstract

本發明提供一種感光性聚醯亞胺組成物，其係包括具有以式(1)所示之結構單元及以式(2)所示之結構單元的聚醯亞胺樹脂、 醌疊氮磺酸鹽、熱硬化劑、以及熱酸產生劑。 式(1)及(2)中，n為10~600的整數，Ar 1為四價有機基團，Ar 2為二至四價有機基團； Ar 3為二價芳基，R 1為一OH基或COOH基。本發明亦提供一種以上述感光性聚醯亞胺組成物製成的光阻膜。

Description

感光性聚醯亞胺組成物及其所製成之光阻膜
本發明係有關於感光性樹脂組成物，特別是有關於可用來製作半導體裝置中的絕緣層或保護層的感光性聚醯亞胺(Photosensitive polyimide，PSPI)組成物。
感光性聚醯亞胺樹脂具有耐熱性、機械物性優異，而且尺寸穩定性也優異，常用於在耐熱性塗層材料領域、印刷電路基板的層間絕緣材料、半導體的絕緣材料等電絕緣材料。然而，傳統的聚醯亞胺樹脂不具耐化學性，故在作為半導體製程中的絶緣層時，常會因後續製程的酸/鹼環境而受損。
本發明的目的之一，即在改善上述聚醯亞胺樹脂的缺點，提供一種感光性樹脂組成物，使其在硬烤之後不但具有耐熱性，也具良好的耐化學性。
本發明提供一種正型感光性樹脂組成物，其係包括具有以式(1)所示之結構單元及以式(2)所示之結構單元的聚醯亞胺樹脂、 醌疊氮磺酸鹽、熱硬化劑、以及熱酸產生劑。 式(1)及(2)中，n 為10~600的整數，Ar 1為四價有機基團，Ar 2為二至四價有機基團； Ar 3為二價芳基，R 1為一OH基或COOH基。
在本發明的一實施例中，相對於聚醯亞胺樹脂100重量份， 醌疊氮磺酸鹽為10~30重量份。
在本發明的一實施例中，相對於聚醯亞胺樹脂100重量份，熱硬化劑為10~50重量份。
在本發明的一實施例中，熱硬化劑可包括環氧系化合物及三聚氰胺系化合物。環氧系化合物與三聚氰胺系化合物的重量比例可為3:1~4:3。
在本發明的一實施例中，熱酸產生劑係為鋶鎓鹽。
在本發明的一實施例中，相對於聚醯亞胺樹脂100重量份，熱酸產生劑為1〜5重量份。
在本發明的一實施例中，鋶鎓鹽為選自由氯化物、溴化物、對甲苯磺酸鹽、三氟甲烷磺酸鹽、四氟硼酸鹽、四(五氟苯基)硼酸鹽、四(五氟苯基)鎵酸鹽、六氟磷酸鹽、六氟砷酸鹽、及六氟銻酸鹽所組成族群中之至少一種。
本發明亦提供一種以上述感光性聚醯亞胺組成物製成的光阻膜。
本發明所提供的感光性聚醯亞胺組成物為一種正型感光性樹脂組成物，主要係包含聚醯亞胺樹脂、作為感光劑的醌疊氮磺酸鹽、熱硬化劑、以及熱酸產生劑。如此成份的組成物在硬烤之後不但具有耐熱性，也具良好的耐化學性，更能滿足特殊規格需求的絕緣層之製造要求。
本發明所使用的聚醯亞胺樹脂，較佳為具有以式(1)所示之結構單元及以式(2)所示之結構單元。 式(1)及(2)中，n 為10~600的整數，該聚醯亞胺樹脂分子量範圍在5000-50000之間，Ar 1為四價有機基團，Ar 2為二至四價有機基團； Ar 3為二價芳基，R 1為一OH基或COOH基。 Ar 1為 Ar 2為 Ar 3為 例如，本發明之聚醯亞胺樹脂較佳為以下式(3)的化學式，式(3)中 ，n為10~600的整數： (3)
本發明所使用的感光劑可為醌疊氮磺酸鹽，例如重氮萘醌。相對於聚醯亞胺樹脂100重量份， 醌疊氮磺酸鹽為10~30重量份。
熱硬化劑的調配量相對於聚醯亞胺樹脂100重量份為10~50重量份，特別係以20~30重量份為佳。熱硬化劑可包括環氧系化合物及三聚氰胺(Melamine)系化合物。環氧系化合物與三聚氰胺系化合物的重量比例可為3:1~4:3。
上述三聚氰胺系化合物可為但不限於三聚氰胺、六羥甲基三聚氰胺六甲基醚、六羥甲基三聚氰胺六丁基醚、四甲氧基甲基苯并胍胺、四丁氧基甲基苯并胍胺等的其中之一或二種以上的組合。較佳為三聚氰胺。
上述環氧系化合物可為但不限於酚醛清漆型環氧樹脂、雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、三酚基丙烷三縮水甘油醚等之三苯基甲烷型環氧樹脂、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯等之環狀脂肪族環氧樹脂、二縮水甘油基酞酸酯、二縮水甘油基六氫酞酸酯、二甲基縮水甘油基酞酸酯等之縮水甘油基酯系樹脂、四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯酚、二縮水甘油基苯胺、二縮水甘油基甲苯胺、四縮水甘油基雙胺基甲基環己烷等之縮水甘油基胺系樹脂等的其中一種或其組合。較佳為三縮水甘油基對胺基苯酚、及雙酚A二縮水甘油醚。
本發明的感光性聚醯亞胺組成物之重要特點之一為添加了熱酸產生劑。熱酸產生劑可選用鋶鎓鹽。在調配量方面，相對於聚醯亞胺樹脂為100重量份，熱酸產生劑可約佔1〜5重量份。在一實施例中，熱鋶鎓塩可選自但不限定於氯化物、溴化物、對甲苯磺酸鹽、三氟甲烷磺酸鹽、四氟硼酸鹽、四(五氟苯基)硼酸鹽、四(五氟苯基)鎵酸鹽、六氟磷酸鹽、六氟砷酸鹽、及六氟銻酸鹽中之至少一種。較佳為六氟磷酸鹽、四(五氟苯基)硼酸鹽。
上述組成物的各成分可溶於有機溶劑中。所選用的有機溶劑可為但不限定於γ-丁內酯 (GBL, gamma-Butyrolactone)，其重量約佔本發明的正型感光性聚醯亞胺組合物之總重的55%-85%。有機溶劑亦可使用目前常為業界使用的N-甲基吡咯烷酮、二甲基乙醯胺、甲基甲醯胺等溶解能力強的極性溶劑有機溶劑，但只溶解於N-甲基吡咯烷酮等含氮系極性溶劑等的醯亞胺樹脂存在由吸濕性導致的白化等問題，保存穩定性不充分。因此，使用該樹脂得到的塗膜(薄膜)會產生無法得到醯亞胺樹脂本來所具有的強韌的塗膜、優異的電特性等的問題。因此可溶于γ-丁內酯等溶解能力較弱的有機溶劑的醯亞胺樹脂是更優選的。
本發明的感光性聚醯亞胺組成物，如上所述，可以溶液的型態存在，以經預烤、曝光、顯影、後烤等程序而得的光阻膜，膜厚的範圍約可在1μm～10μm之間。預烤溫度約為100 ℃~120 ℃，後烤溫度約為200 ℃~250 ℃。本發明的感光性聚醯亞胺組成物溶液的配製，為先配製適量的聚醯亞胺溶液，加入所需的感光劑、熱硬化劑及熱酸產生劑等成份，並加入溶劑以將感光性聚醯亞胺組成物溶液稀釋至所需濃度，以備後續的使用。需注意者，本文所提到的光阻膜，乃泛稱半導體裝置中的絕緣層或保護層等結構，特別是可用於鹼性水溶性顯影，並可廣泛運用於半導體及顯示器產業、晶片封裝，顯示器絕緣層及IC晶片保護層。
聚醯亞胺樹脂的配製例
使用配備有一機械攪拌器與氮氣進口之1000毫升之三頸圓底燒瓶，加入18.3公克(50毫莫耳)之六氟-2,2-二(3胺基-4-羥苯基)(Hexofluoro-2,2-bis(3-amino-4-hydroxyphenyl))、12.3公克(30毫莫耳)之2,2-二(4-(4-胺基苯氧基)苯基)丙烷(2,2-bis(4-(4-aminophenoxyl)phenyl)propane)、2.02公克(10毫莫耳)之4,4’-氧二苯胺(4,4’-Oxydianiline)、20.5公克(50毫莫耳)之TMEG及15.5公克(50毫莫耳)之雙(3,4-二羧苯基)醚二酐(bis(3,4-dicarboxyphenyl)ether dianhydride)，並加入400克之N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone)溶劑。將上述溶液於0℃攪拌4小時後，再加入2.18克(20毫莫耳)之封端劑3-胺基苯醇(3-aminophenol)，並於室溫下再攪拌4小時，再加入80克之二甲苯後升溫至180℃攪拌3小時。冷卻後可得到黏稠聚醯亞胺樹脂。
取前述聚醯亞胺樹脂100重量份以表1的配方比例製作實施例1~實施例3、及比較例1~比較例4之感光性聚醯亞胺組成物。為了驗證本發明的感光性聚醯亞胺組成物所製成的光阻膜的耐化學性、及絕緣性，將各種不同成份的組合物以表2的製程條件製成光阻膜，以進行耐化實驗、及絕緣性測試。其中TMAH2.38 wt%為作為顯影劑之四甲基氫氧化銨的濃度。
表1
鹼可溶樹脂 感光劑 熱硬化劑-1 熱硬化劑-2 熱酸產生劑 溶劑
實施例1 聚醯亞胺樹脂 100% 重氮萘醌20% 三聚氰胺 5% 三縮水甘油基對胺基苯酚15% SIB3 1% γ-丁內酯
實施例2 聚醯亞胺樹脂100% 重氮萘醌20% 三聚氰胺 5% 雙酚A二縮水甘油醚15% SIB3 1% γ-丁內酯
實施例3 聚醯亞胺樹脂100% 重氮萘醌20% 三聚氰胺 5% 三縮水甘油基對胺基苯酚 15% 六氟磷酸鹽 1% γ-丁內酯
比較例1 酚醛樹脂 100% 重氮萘醌20% 三聚氰胺 5% 三縮水甘油基對胺基苯酚15% SIB3 1% γ-丁內酯
比較例2 聚醯亞胺樹脂100% 重氮萘醌20% 三聚氰胺 5% 三縮水甘油基對胺基苯酚15% NA γ-丁內酯
比較例3 聚醯亞胺樹脂100% 重氮萘醌20% 三聚氰胺 20% NA SIB3 1% γ-丁內酯
比較例4 聚醯亞胺樹脂100% 重氮萘醌20% NA 三縮水甘油基對胺基苯酚20% SIB3 1% γ-丁內酯
耐化測試程序
將上述製程製備的光阻膜先測量膜厚，得到(T 0)，將後烤後的光阻膜浸於25℃，75%濃硝酸中1分鐘，然後浸於25℃丙酮20分鐘，再浸於25℃，75%濃硝酸1分鐘，測量膜厚(T A)，觀察殘膜率(T A/ T 0)，殘膜率是指耐化測試結束後所殘留的膜厚與後烤後的膜厚之比值。各種不同成份組成物所製成的光阻膜的耐化測試結果列於表3，其中的SIB3係代表四(五氟苯基)硼酸鹽。
絕緣性測試
使用4339B高電阻計(安捷倫製造)量測上述製程製備的光阻膜膜的表面電阻值(Ω)，以R s表示、及體積電阻值(Ω)，以R v表示，結果如下表3所表示。
表2
膜厚 預烤 曝光 顯影 後烤
2.5μm 100℃/2分鐘 150mJ 30秒(TMAH 2.38 wt%) 200℃/1 小時
表3
殘膜率 Rs Rv
實施例1 96.3% 6.37E+16 3.25E+17
實施例2 96.0% 5.98E+16 2.74E+17
實施例3 97.6% 6.51E+16 3.83E+17
比較例1 70.3% 4.73E+16 1.55E+17
比較例2 63.5% 3.91E+16 1.47E+17
比較例3 51.9% 3.51E+16 2.06E+17
比較例4 75.2% 4.82E+16 1.89E+17
以上的測試證明了本發明的感光性聚醯亞胺組合物所製成的光阻膜具有優異的耐化學性，其中熱硬化劑及熱酸產生劑的適當選用及調配，更有助於提昇光阻膜的耐化學性。
綜上所述，本發明提供一種正型感光性聚醯亞胺組合物，可用於鹼性水溶性顯影，並可廣泛運用於半導體及顯示器產業、晶片封裝，顯示器絕緣層及IC晶片保護層。其具有高感度，良好的解析度，低的硬烤溫度，高膜厚保持率，高耐溶劑性，也具有優異的熱安定性及良好的機械、電器及化學性質，相較於聚醯亞胺有更高的產品良率且可簡化製程，降低成本。
雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。

Claims (10)

  1. 一種感光性聚醯亞胺組成物，其係包括具有以式(1)所示之結構單元及以式(2)所示之結構單元的聚醯亞胺樹脂、醌疊氮磺酸鹽、熱硬化劑、以及熱酸產生劑， 式(1)及(2)中，n為10~600的整數，Ar1為四價有機基團，Ar2為二至四價有機基團；Ar3為二價芳基，R1為一OH基或COOH基；其中該熱硬化劑係包括環氧系化合物及三聚氰胺系化合物，該環氧系化合物與該三聚氰胺系化合物的重量比例為3：1~4：3。
  2. 如請求項1所述之感光性聚醯亞胺組成物，其中相對於該聚醯亞胺樹脂100重量份，該醌疊氮磺酸鹽為10~30重量份。
  3. 如請求項1所述之感光性聚醯亞胺組成物，其中相對於該聚醯亞胺樹脂100重量份，該熱硬化劑為10~50重量份。
  4. 如請求項3所述之感光性聚醯亞胺組成物，其中該熱酸產生劑係為鋶鎓鹽。
  5. 如請求項4所述之感光性聚醯亞胺組成物，其中相對於該聚醯亞胺樹脂100重量份，該熱酸產生劑為1~5重量份。
  6. 如請求項4所述之感光性聚醯亞胺組成物，其中該鋶鎓鹽為選自由氯化物、溴化物、對甲苯磺酸鹽、三氟甲烷磺酸鹽、四氟硼酸鹽、四(五氟苯基)硼酸鹽、四(五氟苯基)鎵酸鹽、六氟磷酸鹽、六氟砷酸鹽、及六氟銻酸鹽所組成族群中之至少一種。
  7. 如請求項1所述之感光性聚醯亞胺組成物，其中該聚醯亞胺樹脂為式(3)所示之結構，式(3)中，n為10~600的整數。
  8. 一種光阻膜之製造方法，其係包括：將如請求項1至7項中的任一項所述之感光性聚醯亞胺組成物塗佈於基板；對該感光性聚醯亞胺組成物進行曝光；以及進行顯影。
  9. 如請求項8所述之光阻膜之製造方法，其中於對該感光性聚醯亞胺組成物進行曝光之前，更包括以100℃~120℃進行預烤。
  10. 如請求項8所述之光阻膜之製造方法，其中於進行顯影之後，更包括以200℃~250℃進行後烤。
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