TWI618979B - 導熱型聚醯亞胺基板 - Google Patents

導熱型聚醯亞胺基板 Download PDF

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Publication number
TWI618979B
TWI618979B TW106121965A TW106121965A TWI618979B TW I618979 B TWI618979 B TW I618979B TW 106121965 A TW106121965 A TW 106121965A TW 106121965 A TW106121965 A TW 106121965A TW I618979 B TWI618979 B TW I618979B
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Taiwan
Prior art keywords
thermally conductive
photosensitive resin
item
patent application
polyfluorene imide
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TW106121965A
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English (en)
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TW201905590A (zh
Inventor
黃堂傑
陳伯誠
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律勝科技股份有限公司
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Priority to TW106121965A priority Critical patent/TWI618979B/zh
Priority to CN201810208818.0A priority patent/CN109203596B/zh
Application granted granted Critical
Publication of TWI618979B publication Critical patent/TWI618979B/zh
Priority to US15/928,994 priority patent/US10953641B2/en
Publication of TW201905590A publication Critical patent/TW201905590A/zh

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Abstract

本發明提供一種導熱型聚醯亞胺基板，其包含至少1層之絕緣層，且此些絕緣層的單面或兩面上有金屬層。絕緣層之材料為導熱係數介於0.4-2的導熱型感光性樹脂，且導熱型感光性樹脂包括下列成分：(a)感光性聚醯亞胺、(b)無機填充劑以及(c)二氧化矽溶液。感光性聚醯亞胺之含量佔導熱型感光性樹脂之固體成分總重的50-80%。無機填充劑佔導熱型感光性樹脂固體成分總重的20-50%，且粒徑介於40nm至5μm。二氧化矽溶液包含溶膠凝膠方式聚成的二氧化矽顆粒，顆粒之粒徑介於10-15nm，且含量佔該導熱型感光性樹脂之固體成分總重的5-30%。

Description

導熱型聚醯亞胺基板
本發明揭示一種聚醯亞胺基板，特別是關於一種使用導熱型感光性聚醯亞胺樹脂作為絕緣層的聚醯亞胺基板。
一般來說，聚醯亞胺樹脂係由芳香族的四羧酸或其衍生物與芳香二胺、芳香二異氰酸酯縮聚而製備，製備所得的聚醯亞胺樹脂具有優良的耐熱性、耐化學性、機械和電特性，因而被廣泛用於如半導體密封劑等絕緣耐熱之電子材料。
聚醯亞胺應用於半導體元件的製程中，往往需要利用微影成像技術(Micro Lithography)來製作線路圖形，如果使用傳統的聚醯亞胺，則必須額外加入一層光阻材料(photoresist)以進行蝕刻。因此，感光性聚醯亞胺(Photosensitive polyimide，PSPI)由於同時具有光阻及絕緣保護材料的特性，可以簡化製程，使得軟板電子材料製程有相當的進步，目前是相當熱門的尖端材料。
然而，由於近年電路設計越趨密集，電路中所產生之熱能累積，造成產品過熱，成為亟欲解決的問題。目前市面上使用熱傳導係數較低之聚醯 亞胺製作的多層基板已無法滿足產業需求。
本發明目的在於提供一種具有高導熱係數同時具良好感光性的導熱型感光性樹脂，以及使用其之導熱型聚醯亞胺基板。
根據本發明之一實施例，提供一種導熱型聚醯亞胺基板。導熱型聚醯亞胺基板包含至少1層之絕緣層，且在絕緣層的單面或兩面上有金屬層。絕緣層之材料為導熱係數介於0.4-2的導熱型感光性樹脂，且導熱型感光性樹脂包括下列成分：(a)感光性聚醯亞胺、(b)無機填充劑以及(c)二氧化矽溶液。
感光性聚醯亞胺為下式(1)之重複單元所構成之聚合物或共聚合物：
其中，m、n各自獨立為10至600；X為四價有機基團，其主鏈部份含脂肪環基團(alicyclic compound group)且脂肪族基團占總組成之60-80%；Y為二價有機基團，其主鏈部份含矽氧烷基團(polydimethylsiloxane group)；Z為二價有機基團，其支鏈部份至少含酚基(phenoilc hydroxyl group)或羧基(carboxyl group)。此感光性聚醯亞胺之含量佔導熱型感光性樹脂之固體成分總重的50-80%。
無機填充劑，選自氧化鋁、石墨烯、無機粘土、雲母粉、氮化硼、氮化鋁、二氧化矽、氧化鋅、氧化鋯、奈米碳管及奈米碳纖維中的至少一種， 此無機填充劑之含量佔導熱型感光性樹脂固體成分總重的20-50%，且粒徑介於40nm至5μm。
二氧化矽溶液，其包含溶膠凝膠方式聚成的二氧化矽顆粒，二氧化矽顆粒之粒徑介於10-15nm，且含量佔該導熱型感光性樹脂之固體成分總重的5-30%。
一實施例中，上述導熱型感光性樹脂之成分更包括一丙烯酸樹脂(acrylic resin)光交聯劑。此丙烯酸樹脂之含量佔導熱型感光性樹脂固體成分總重的5-40%。
一實施例中，上述導熱型感光性樹脂之成分更包括一熱交聯劑。此熱交聯劑包括酚類化合物、烷氧甲基胺樹脂或環氧樹脂，且含量佔該導熱型感光性樹脂固體成分總重的5-40%。
一實施例中，無機填充劑為氮化硼或氮化鋁。
一實施例中，感光性聚醯亞胺式(1)中的X係為下列基團其中之一：
一實施例中，感光性聚醯亞胺式(1)中的Y係為下列基團： 其中p=0-20。
一實施例中，感光性聚醯亞胺式(1)中的Z係為下列基團其中之一：
一實施例中，二氧化矽溶液中的二氧化矽顆粒佔此導熱型感光性樹脂固體成分總重的7.5-15%，且粒徑為10-15nm。
一實施例中，導熱型聚醯亞胺基板更具有一電路元件，其位於絕緣層內並連接至少一金屬層。此電路元件包括電性連接墊、金屬柱、金屬連結支架或焊線。
一實施例中，導熱型聚醯亞胺基板更包括一保護層，覆蓋於最外層之金屬層上。保護層的材料包括感光性油墨、熱固性油墨、聚對二唑苯纖維(PBO)、聚苯乙烯-苯並環丁烯共聚物(PSBCB)、感光顯影覆蓋膜(PIC)，或可與絕緣層相同。
一實施例中，導熱型聚醯亞胺基板為多層結構，包括兩層以上的絕緣層，且每一絕緣層的單面或兩面上皆有金屬層。
一實施例中，導熱型聚醯亞胺基板更包括一補強層，其為含浸導熱型 感光性樹脂的碳纖維布。
為使本發明之上述與其他方面更能清楚易懂，下文特舉實施例，並配合所附圖式詳細說明。然需特別注意的是，實施例之成分、配比、結構僅用於示例之用，並非用以限制本發明。
100‧‧‧導熱型聚醯亞胺基板
10‧‧‧基材
20、40‧‧‧金屬層
21‧‧‧電路元件
30‧‧‧絕緣層
31‧‧‧通孔
50‧‧‧保護層
60‧‧‧凸塊
70‧‧‧半導體IC
第1圖繪示本發明之導熱型聚醯亞胺基板的示意圖；第2A圖至第2F圖繪示第1圖之導熱型聚醯亞胺基板的製造方法；第3A圖及第3B圖繪示本發明之導熱型聚醯亞胺基板與傳統聚醯亞胺基板散熱能力的比較結果，其中第3A圖為操作電壓16V的比較結果，第3B圖為操作電壓18V的比較結果。
本發明提供一種導熱型感光性樹脂，其主成分為特定分子結構的感光性聚醯亞胺，並加入無機填充劑來改善導熱係數，再加入二氧化矽溶液提昇光穿透效應，獲得具高導熱係數且感光性優良的聚醯亞胺樹脂。
本發明之導熱型感光性樹脂，其中包含：(a)感光性聚醯亞胺；(b)無機填充劑；以及(c)二氧化矽溶液。其中(a)感光性聚醯亞胺具有下式(1)之結構：
式(1)中，m、n各自獨立為10至600，X為四價有機基團，其主鏈部份 含脂環族基團(alicyclic compound group)，包含(但不限於)以下基團或其組合：
Y為二價有機基團，較佳者包含(但不限於)以下基團： p=0-20
Y之鏈長以短為佳(p=0)，最長可到p=20，過長將破壞感光性聚醯亞胺之性質。
Z為二價有機基團，其支鏈部份具有酚基(phenolic hydroxyl group)或羧基(carboxyl group)，酚基或羧基的含量約佔聚醯亞胺莫耳數之10-30%。調整支鏈酚基、羧基的含量可以控制顯影的時間，當支鏈酚基或羧基的含量較高，則鹼性顯影液對感光性聚醯亞胺的溶解性較佳，可提升其顯影性。
Z可包括但不限於下列基團：
(a)感光性聚醯亞胺之含量較佳係佔導熱型感光性樹脂固體成分總重的50-80%。
本發明之導熱型感光性樹脂還包含(b)無機填充劑，其主要目的為增進聚醯亞胺樹脂之導熱性。無機填充劑可選自氧化鋁、石墨烯、無機黏土、雲母粉、氮化硼、二氧化矽、氮化鋁、氧化鋅、氧化鋯、奈米碳管及奈米碳纖維中的一種或多種，且其粒徑較佳介於40nm至5μm。無機填充劑之含量較佳佔導熱型感光性樹脂固體成分總重的20-50%。
此外，本發明之導熱型感光性樹脂中更添加了(c)二氧化矽溶液(silica solution,colloidal silica)，其包含溶膠凝膠(Sol gel)方式聚成的奈米級二氧化矽顆粒，例如Nissan Chemical之DMAC-ST，二氧化矽顆粒粒徑為10-15nm。二氧化矽溶液中之二氧化矽顆粒的含量較佳佔導熱型感光性樹脂之固體成分總重的5-30%。本發明藉由添加這兩種不同粒徑的填充劑，利用小粒徑之二氧化矽顆粒將相對大粒徑之無機填充劑隔開，使膠體內部於曝光時不至於被大粒徑之無機導熱填充劑遮蓋，可在提昇導熱能力的同時，維持感光性聚醯亞胺的解析度。
本發明之導熱型感光性樹脂另可加入結構具有酚類化合物或烷氧甲基胺樹脂的熱交聯劑，使聚烯亞胺分子鏈上的末端基在曝光烘烤時與熱交聯劑形成交聯結構；亦可加入丙烯酸樹脂光交聯劑，在曝光後產生酸而形成 酸催化交聯機制。如此產生的交聯結構可增加導熱型感光性樹脂的耐化性及成膜性。
熱交聯劑其主要目的為在曝後硬烤時經由酸催化及熱處理，與PI主鏈-OH基或末端上-OH基的鄰位產生交聯，使曝光區域與未曝光區域產生溶解性上的差異，進而快速形成圖案。熱交聯劑含量約佔導熱型感光性樹脂固體成分總重之5-40%，若低於5%，則其交聯不足且不耐化學溶劑；若超過40%，則顯影性較差。
光交聯劑在曝光後會吸收一定波長的光能後產生自由基，引發或催化相應的單體或預聚物的聚合而形成交聯。其添加量為導熱型感光性樹脂固體成分總重之5-40%，若低於5%，則其感光度不足；若超過40%，則顯影性較差。
感光性聚醯亞胺的合成步驟為將適量的二胺單體與二酸酐單體溶於N-甲基吡咯烷酮(1-Methyl-2-pyrrolidone；NMP)中，於80℃下反應2小時，加入二甲苯(Xylene)並加熱至180℃將其餾出。再加入含有酚基或羧基之二胺單體，於80℃下反應2小時，加入二甲苯並加熱至180℃將其餾出，約4小時後將其冷卻。導熱型感光性樹脂的製作方法係取上述製作完成的感光性聚醯亞胺膠體，加入無機填充劑、二氧化矽溶液、光交聯劑及熱交聯劑即可得本發明之導熱型感光性樹脂(光交聯劑及熱交聯劑可選擇性加入)。
實施例1
取一配備有機械攪拌器與氮氣進入口之500ml三頸圓底燒瓶，加入 19.88g(80毫莫耳)之1,3-雙(3-氨基丙基)-1,1,3,3-四甲基二矽氧烷(1,3-Bis(3-aminopropyl)tetramethyldisiloxane)、80.7g之N-甲基吡咯烷酮(1-Methyl-2-pyrrolidone；NMP)、39.68g(160毫莫耳)之二環[2,2,2]辛-7-烯-2,3,5,6-四酸二酐(Bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride)將上述溶液於50-80℃反應2小時後，加入45g之二甲苯後升溫至180℃後持續攪拌1.5小時，再加入21.14g(80毫莫耳)之3,5-二氨基苯甲酸2-(2-甲基丙烯醯氧基)乙基酯(2-(Methacryloyloxy)ethyl 3,5-diaminobenzoate)，將上述溶液於50-80℃反應2小時後，加入50g之二甲苯後升溫至180℃後持續攪拌4小時。冷卻後即可得PIA-1溶液。取PIA-1溶液50g，加入11.38g之甲基丙烯酸縮水甘油酯(Glycidyl methacrylate；GMA)並於70-100℃下攪拌24小時，可得式(1)之感光性聚醯亞胺PSPI-1。
式(1)之PSPI-1中，X為；Y為， p=0；Z為；且m=n=120。
取75g PSPI-1加入9.375g填充劑1μm氮化硼(Boron Nitride)，再加入23.43g 20%二氧化矽溶液(Nissan Chemical之DMAC-ST，其二氧化矽顆粒粒徑為10-15nm)均勻混合，可得導熱型感光性樹脂PSPI-BN1。利用線棒 塗佈PSPI-BN1於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
實施例2
將實施例1中的PSPI-1溶液加入12.5g填充劑1μm氮化硼(Boron Nitride)，再加入25g 20%二氧化矽溶液(顆粒粒徑為10-15nm)均勻混合，可得導熱型感光性樹脂PSPI-BN2。利用線棒塗佈PSPI-BN2於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
實施例3
將實施例1中的PSPI-1溶液加入16.07g填充劑1μm氮化硼(Boron Nitride)，再加入26.78g 20%二氧化矽溶液(顆粒粒徑為10-15nm)均勻混合，可得導熱型感光性樹脂PSPI-BN3。利用線棒塗佈PSPI-BN3於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。 接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
實施例4
將實施例1中的PSPI-1溶液加入16.07g填充劑50nm氮化硼(Boron Nitride)，再加入26.78g 20%二氧化矽溶液(顆粒粒徑為10-15nm)均勻混合，可得導熱型感光性樹脂PSPI-BN4。利用線棒塗佈PSPI-BN4於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
實施例5
將實施例1中的PSPI-1溶液加入12.5g填充劑5μm氮化鋁(Aluminium Nitride)，再加入25g 20%二氧化矽溶液(顆粒粒徑為10-15nm)均勻混合，可得導熱型感光性樹脂PSPI-BN5。利用線棒塗佈PSPI-BN2於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
比較例1
將實施例1中的PSPI-1溶液加入9.375g填充劑1μm氮化硼(Boron Nitride)均勻混合，可得導熱型感光性樹脂PSPI-CT1。利用線棒塗佈PSPI-CT1於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
比較例2
將實施例1中的PSPI-1溶液加入12.5g填充劑1μm氮化硼(Boron Nitride)均勻混合，可得導熱型感光性樹脂PSPI-CT2。利用線棒塗佈PSPI-CT2於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
比較例3
將實施例1中的PSPI-1溶液加入16.07g填充劑1μm氮化硼(Boron Nitride)均勻混合，可得導熱型感光性樹脂PSPI-CT3。利用線棒塗佈PSPI-CT3於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以 1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
比較例4
將實施例1中的PSPI-1溶液加入16.07g填充劑50nm氮化硼(Boron Nitride)均勻混合，可得導熱型感光性樹脂PSPI-CT4。利用線棒塗佈PSPI-CT4於基材上，經90℃烘箱下，8分鐘之預烤程序後，可得膜厚約15μm之薄膜，並以曝光機(功率7kw)投以約400mJ/cm2之能量加以曝光，再以1wt%(重量百分比)碳酸鈉(Sodium carbonate)顯影劑加以顯影，顯影時間為1分鐘。接著在氮氣烘箱200℃下進行2小時的硬烤程序，便可得到耐熱性之顯影圖形。
實施例1-5和比較例1-4的導熱型感光性樹脂其配方及特性如表一所示：
表一中，填充劑佔比係指無機填充劑重量佔導熱型感光樹脂之固體含量的百分比，計算公式如下：%填充劑=(W填充劑/Wsolid)×100%
固體含量(%solid)測量方法為，取適當重量膠體，秤重後使用200℃烘烤90分鐘，烘烤後再次秤重得固體重量(Wsolid)。得知固體重量後，固體含量可由以下公式計算而得：%solid=(Wsolid/Wtotal)×100%
以實施例2之導熱型感光樹脂PSPI-BN2為例，其為聚醯亞胺PSPI-1 75g(固體含量50%)添加12.5g無機填充劑氮化硼，故無機填充劑佔比(%填充劑)=
本發明之導熱型感光樹脂組成物實施例1-4，係為相同的感光性聚醯亞胺加入不同重量百分比(wt%)之無機填充劑，且添加相同重量百分比之奈米級二氧化矽顆粒(以二氧化矽溶液方式添加)。相對的，比較例1-4係為相同的感光性聚醯亞胺加入不同重量百分比(wt%)之無機填充劑，但未添加二氧化矽溶液。由表一可知，加入二氧化矽溶液，具有不同粒徑之填充劑的實施例1-4，，比起僅加入單一一種無機填充劑的比較例1-4，其導熱係數、熱阻(熱阻越小越好)與解析度表現(解析度越小越好)皆較佳。更甚者，比較例3之雖然主成分也是感光性聚醯亞胺，但由於僅添加一種無機填充劑，且添加比例過高，導致根本無法顯影。另外，比較例3雖然使用了粒徑較小(50nm)的無機填充劑，但由於添加比例過高，且未添加 二氧化矽溶液，仍然無法顯影，且導熱係數與熱阻都較差。實施例5使用另外一種無機填充劑(氮化鋁)與二氧化矽溶液混合，同樣能夠獲得高導熱、低熱阻、解析度優良的效果。本發明藉由添加較大粒徑的無機填充劑，以及粒徑較小的二氧化矽溶液，利用小粒徑之二氧化矽顆粒將相對大粒徑之無機填充劑隔開，使膠體內部於曝光時不至於被大粒徑之無機導熱填充劑遮蓋，可獲得具高導熱係數且感光性優良的導熱型感光性樹脂。
導熱型聚醯亞胺基板
本發明導熱型感光性樹脂由於兼具導熱效果良好以及高感光性的優點，可有多種用途。例如可以作為薄型化基板、載板的介電材料，用以製作多層的疊構基板。
第1圖為本發明之導熱型聚醯亞胺的示意圖。導熱型聚醯亞胺基板100之結構包括基材10、金屬層20,40、電路元件21、絕緣層30以及保護層50。導熱型聚醯亞胺基板100可作為半導體元件之載板，藉由錫鉛凸塊60(solder bump)連結半導體IC 70。
以下藉由第2A圖至第2F圖說明導熱型聚醯亞胺基板100的製造方式。首先如第1圖所示，提供基材10。基材10的材料可包括BT樹脂基板、FR-4基板、FR-5基板、ABF樹脂基板或FCCL軟性銅箔基板等，亦可為含浸導熱型感光性樹脂的碳纖維布，作為加強導熱型聚醯亞胺基板強度的補強層。本發明並不對此限制。基材10的上下皆具有金屬層20，其材質可為銅或其他導電材料。
接著如第2B圖所示，圖案化(patterning)上下金屬層20，形成電路 設計所需之樣式。圖案化之方式可為習知的黃光微影製程，本發明並不限制。
一實施例中，如第2C圖所示，圖案化的金屬層20上可放置電路元件21，其可為被動元件、主動元件、電性連接墊、金屬柱、金屬連結支架或焊線等。
接著，如第2D圖所示，於基材10及金屬層20上形成絕緣層30。絕緣層之材料即為前述之導熱型感光性樹脂，其可直接曝光顯影，而不需要額外使用光阻材料來圖案化，且具有高導熱性，可降低基板的溫度。絕緣層30可用印刷、旋塗、輥塗(roller coating)或壓貼合(laminating)等方式形成，並使用UV光曝光，再以顯影劑去除的方式進行圖案化形成通孔31。
然後，如第2E圖所示，在絕緣層30上形成另外一層圖案化金屬層40。圖案化金屬層較佳的製作方法是先對絕緣層30與通孔31進行表面金屬化，形成一薄金屬層使其成為後續製程之金屬形成基底，並增加附著力。然後再以電鍍的方式於特定地方加厚金屬，形成電路設計所需樣式的圖案化金屬層40。
最後，如第2F圖所示，在最外層的金屬層20、40上形成保護層50，圖案化使內部的金屬層外露，再將金屬層外露的部份與半導體IC 70電性連接，便完成第1圖所示導熱型聚醯亞胺基板100。第2F圖中所示之金屬電性連接之方式為覆晶(Flip Chip)與錫鉛凸塊60(Solder Bump)，然亦可採用如打線連結(wire bonding)等的其他方式，本發明並不限制。保護層50的材料可與絕緣層30相同，使用本發明之導熱型感光性樹脂，亦可使用感 光性油墨、熱固性油墨、聚對二唑苯纖維(PBO)、聚苯乙烯-苯並環丁烯共聚物(PSBCB)或感光顯影覆蓋膜(PIC)。
第1圖之導熱型聚醯亞胺基板100包括2層金屬層20、40，於其他實施例中，可重複第2D圖至第2F圖的增層結構製程，便可製作出更多層數的導熱型聚醯亞胺基板。
另外，本發明之導熱型聚醯亞胺基板並不限定必須依上述製程製造，亦可使用其他習知的半導體製程。只要複數金屬層之間的絕緣層係使用本發明所述的導熱型感光性樹脂，皆屬本發明之範圍。
第3A圖及3B圖比較傳統聚醯亞胺基板與本發明導熱型聚醯亞胺基板的散熱能力。其係將相同的發熱元件分別設置在傳統PSPI基板(單純使用PSPI作為絕緣層)，以及使用本發明之導熱型感光性樹脂作為絕緣層的基板中，再用紅外線溫度掃描儀量測基板的工作溫度。圖中使用了本發明實施例3、5以及比較例4的導熱型感光性樹脂，第3A圖為操作電壓16V的測試結果，第3B圖為操作電壓18V的測試結果。由圖可知，使用單一填充劑的聚醯亞胺基板(比較例2，導熱係數0.19)，其散熱效果較一般的PSPI基板(導熱係數約0.1-0.2)好，但並沒有很明顯之差異。而使用本發明之導熱型感光性樹脂(實施例3、5)的導熱型聚醯亞胺基板，其工作溫度跟傳統聚醯亞胺基板相較有極大差異，當操作電壓較高時，差異更為明顯，甚至降低達40%之多(90℃至55℃)。
本發明之導熱型聚醯亞胺基板，由於使用了導熱型感光性樹脂，其工作溫度比起傳統的PSPI基板(導熱係數0.1-0.2)大幅降低，且由於仍保有感光性，圖案化製程時不需要額外使用光阻，可簡化製程、增加良率。
雖然本發明以實施例說明如上，惟此些實施例並非用以限制本發明。本領域之通常知識者在不脫離本發明技藝精神的範疇內，當可對此些實施例進行等效實施或變更，故本發明的保護範圍應以其後所附之申請專利範圍為準。
100‧‧‧導熱型聚醯亞胺基板
10‧‧‧基材
20、40‧‧‧金屬層
21‧‧‧電路元件
50‧‧‧保護層
60‧‧‧凸塊
70‧‧‧半導體IC

Claims (15)

  1. 一種導熱型聚醯亞胺基板，包含：至少一層之絕緣層，且在該些絕緣層的單面或兩面上有金屬層；該絕緣層之材料為導熱係數介於0.4-2的導熱型感光性樹脂，且該導熱型感光性樹脂包括下列成分：(a)感光性聚醯亞胺，其為下式(1)之重複單元所構成之聚合物或共聚合物： 其中，m、n各自獨立為10至600；X為四價有機基團，其主鏈部份含脂肪環基團(alicyclic compound group)；Y為二價有機基團，其主鏈部份含矽氧烷基團(polydimethylsiloxane group)；Z為二價有機基團，其支鏈部份至少含酚基(phenoilc hydroxyl group)或羧基(carboxyl group)，該感光性聚醯亞胺之含量佔該導熱型感光性樹脂之固體成分總重的50-70%；(b)無機填充劑，選自氧化鋁、石墨烯、無機粘土、雲母粉、氮化硼、氮化鋁、二氧化矽、氧化鋅、氧化鋯、奈米碳管及奈米碳纖維中的至少一種，該無機填充劑之含量佔該導熱型感光性樹脂固體成分總重的20-30%，且粒徑介於40nm至5μm；以及(c)二氧化矽溶液，其包含溶膠凝膠方式聚成的二氧化矽顆粒，該些二氧化矽顆粒之粒徑介於10-15nm，且該些二氧化矽顆粒含量佔該導熱型 感光性樹脂之固體成分總重的5-30%。
  2. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂的成分更包括一含丙烯酸樹脂(acrylic resin)之光交聯劑。
  3. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂的成分更包括一熱交聯劑，該熱交聯劑包括酚類化合物、烷氧甲基胺樹脂或環氧樹脂。
  4. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂中的該無機填充劑為氮化硼或氮化鋁。
  5. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂中的X係為下列基團其中之一：
  6. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂中的Y係為下列基團：其中p=0-20。
  7. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂中的Z係為下列基團其中之一：
  8. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中該導熱型感光性樹脂內的該些二氧化矽顆粒佔該導熱型感光性樹脂固體成分總重的7.5-15%，且粒徑為10-15nm。
  9. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，更包括一電路元件，其位於絕緣層內並連接至少一個該金屬層。
  10. 如申請專利範圍第9項所述之導熱型聚醯亞胺基板，其中該電路元件包括電性連接墊、金屬柱、金屬連結支架或焊線。
  11. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，更包括一保護層，該保護層覆蓋於最外層之該金屬層上。
  12. 如申請專利範圍第11項所述之導熱型聚醯亞胺基板，其中該保護層的材料包括感光性油墨、熱固性油墨、聚對二唑苯纖維(PBO)、聚苯 乙烯-苯並環丁烯共聚物(PSBCB)或感光顯影覆蓋膜(PIC)。
  13. 如申請專利範圍第11項所述之導熱型聚醯亞胺基板，其中該保護層的材料與該絕緣層相同。
  14. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其中包括兩層以上的絕緣層，且每一絕緣層的單面或兩面上皆有金屬層。
  15. 如申請專利範圍第1項所述之導熱型聚醯亞胺基板，其更包括一補強層，該補強層為含浸該導熱型感光性樹脂的碳纖維布。
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