TWI665281B - 暫時性接著用組成物以及暫時性接著用溶液 - Google Patents

暫時性接著用組成物以及暫時性接著用溶液 Download PDF

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TWI665281B
TWI665281B TW107109943A TW107109943A TWI665281B TW I665281 B TWI665281 B TW I665281B TW 107109943 A TW107109943 A TW 107109943A TW 107109943 A TW107109943 A TW 107109943A TW I665281 B TWI665281 B TW I665281B
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temporary
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solvent
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張修明
洪宗泰
蕭麗蓉
林博文
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台虹科技股份有限公司
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Abstract

本發明提供一種暫時性接著用組成物以及暫時性接著用溶液。所述暫時性接著用組成物包括二酐單體、吸光單體以及吸光材料。吸光單體包括N,N,N,N-(對氨基苯基)-對苯二胺（DPDA）及N,N-(對氨基苯基)-對苯二胺（TPDA）中的至少一者。吸光材料包括碳黑及二氧化矽。

Description

暫時性接著用組成物以及暫時性接著用溶液
本發明是有關於一種暫時性接著用組成物以及暫時性接著用溶液，且特別是有關於一種含有高吸光性的吸光材料的暫時性接著用組成物以及暫時性接著用溶液。
隨著微電子工業的發展以及電子市場的驅動，半導體封裝技術越來越朝向更小、更輕薄且性能更加優良的趨勢邁進。為了使晶圓在使用中能夠更佳地散熱、延長壽命並有利於後期系統封裝，通常需要將晶圓片的厚度降至100 μm。一般而言，先將晶圓器件暫時性地黏接至較厚的承載玻璃上，通過對晶圓背部進行腐蝕、研磨等處理以減少一定厚度，再通過外界的光、電、熱或力使黏接層失效，而將晶圓器件與承載體分離而完成，其中用來先接著後離型的暫時性接著層對製程是否能夠成功實施具有關鍵性的影響。更詳細而言，暫時性接著層在晶圓增層暫時固定、厚晶圓減薄與裁切暫時固定以及運送暫時固定的情況下，均發揮相當重要的作用。
在習知技術中，暫時性接著層的解黏方式包括UV光照射解黏、溶劑解黏或雷射解黏。UV光照射解黏的耐熱溫度約為120℃，無法耐溫至260℃，容易受到日害影響，造成解黏反應提早發生。溶劑解黏的缺點則為耐溶劑性不佳，因此，可能造成製程上限制，故不符合市場需求。雷射解黏的耐熱性及耐化性較佳，但一般只在波長為355 nm或532 nm的雷射光照射下失去黏著力，較少適用於波長為1064 nm的雷射光，因此，較不易使用紅光雷射解黏。
基於上述，發展出一種藉由雷射吸收降低黏著力的暫時性接著層，以提高雷射光波長吸收度，為目前所需研究的重要課題。
本發明提供一種暫時性接著用組成物，含有高吸光性的吸光材料，具有良好耐熱性、耐化性及密著性，可藉由吸收波長為1064 nm的雷射光降低黏著力。
本發明的暫時性接著用組成物包括二酐單體、吸光單體以及吸光材料，其中吸光單體包括N,N,N,N-(對氨基苯基)-對苯二胺（DPDA）及N,N-(對氨基苯基)-對苯二胺（TPDA）中的至少一者，吸光材料包括碳黑及二氧化矽。
在本發明的一實施例中，二酐單體為2,3,3',4'-二苯醚四甲酸二酐(PDMS)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)以及3,3',4,4'-二苯醚四羧酸二酐(OPDA)的其中一種。
在本發明的一實施例中，以暫時性接著用組成物的總重量計，二酐單體的添加量為10 wt%至40 wt%，吸光單體的添加量為10 wt%至20 wt%，吸光材料的添加量為20 wt%至50 wt%。
在本發明的一實施例中，暫時性接著用組成物更包括溶劑，溶劑包括N-甲基吡咯烷酮（NMP）、二甲基乙醯胺(DMAC)或環己酮。
在本發明的一實施例中，以暫時性接著用組成物的總重量計，溶劑的添加量為10 wt%至60 wt%。
在本發明的一實施例中，暫時性接著用組成物在波長為1064 nm的雷射光照射下失去黏著力。
在本發明的一實施例中，暫時性接著用組成物的耐熱溫度為350℃至450℃。
本發明提供一種暫時性接著用溶液，包括上述暫時性接著用組成物，可採用旋轉塗佈方式塗佈。
在本發明的一實施例中，以溶劑稀釋上述暫時性接著用組成物以製備暫時性接著用溶液，稀釋比例為10%至60%。
基於上述，本發明的暫時性接著用組成物包括耐熱性高的二酐單體以具有良好耐熱性及密著性，同時含有吸光單體（DPDA及TPDA）以提升雷射光波長吸收度，更含有吸光材料（碳黑及二氧化矽）以吸收並折射光線，使得本發明的暫時性接著用組成物可藉由吸收波長為1064 nm的雷射光降低黏著力，更具有良好耐熱性、耐化性及密著性。
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例作詳細說明如下。
在本文中，由「一數值至另一數值」表示的範圍，是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此，某一特定數值範圍的記載，涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍，如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。
本發明提出一種暫時性接著用組成物，可用以製備暫時性接著用溶液，具有耐熱性佳、耐化性佳以及吸濕性低的優點。以下，特舉實施方式作為本發明確實能夠據以實施的範例。 ＜ 暫時性接著用組成物 ＞
本發明的暫時性接著用組成物包括二酐單體、吸光單體、吸光材料以及溶劑。以下，將對上述各種組分進行詳細說明。 ＜ 二酐單體 ＞
在本實施例中，二酐單體包括如下所示之結構的其中一種： 2,3,3',4'-二苯醚四甲酸二酐(PDMS) 結構式(I)、 3,3',4,4'-聯苯四羧酸二酐(BPDA) 結構式(II)、 3,3',4,4'-二苯甲酮四甲酸二酐(BTDA) 結構式(III) 以及 3,3',4,4'-二苯醚四羧酸二酐(OPDA) 結構式(IV)。 以暫時性接著用組成物的總重量計，二酐單體的添加量例如是10 wt%至40 wt%。添加二酐單體可提升暫時性接著用組成物以及後續製成的溶液之耐熱性及密著性，因此，可改善習知UV光照射解黏技術中耐熱性不佳的問題。由於本發明的暫時性接著用組成物含有高耐熱性的二酐單體，耐熱溫度例如是大於260℃，更具體而言例如是350℃至450℃，可高達410℃。 ＜ 吸光單體 ＞
在本實施例中，吸光單體可包括N,N,N,N-(對氨基苯基)-對苯二胺（DPDA）及N,N-(對氨基苯基)-對苯二胺（TPDA）中的至少一者，其可由以下化學結構式表示： DPDA TPDA 以暫時性接著用組成物的總重量計，吸光單體的添加量例如是10 wt%至20 wt%。添加吸光單體可提升雷射光波長吸收度。 ＜ 吸光材料 ＞
在本實施例中，吸光材料可包括碳黑及二氧化矽（SiO 2）。以暫時性接著用組成物的總重量計，吸光材料的添加量例如是20 wt%至50 wt%。添加吸光材料可吸收並折射光線，使得本發明的暫時性接著用組成物可在波長為1064 nm的雷射光照射下失去黏著力，具有容易解黏的特性。相較於習知的雷射解黏技術僅能於在波長為355 nm或532 nm的雷射光照射下解黏，本發明更具有優勢。 ＜ 溶劑 ＞
在本實施例中，溶劑可包括N-甲基吡咯烷酮（NMP）、二甲基乙醯胺(DMAC)或環己酮。以暫時性接著用組成物的總重量計，溶劑的添加量例如是10 wt%至60 wt%。 ＜ 暫時性接著用溶液 ＞
本發明的暫時性接著用溶液包括上述暫時性接著用組成物以及溶劑，可採用旋轉塗佈方式塗佈，塗佈厚度例如是0.5 μm至5 μm。在本實施例中，溶劑可包括N-甲基吡咯烷酮（NMP），以溶劑稀釋上述暫時性接著用組成物以製備暫時性接著用溶液，稀釋比例例如是10 %至60 %。更詳細而言，在塗佈厚度為0.6 μm時，在波長為1064 nm的雷射光照射下，吸收度Abs為約1.8，穿透度為約2 %。
以下，藉由實驗例來詳細說明上述實施例的暫時性接著用組成物及所製成的溶液。然而，下述實驗例並非用以限制本發明。 實驗例
為了證明本發明所提出的暫時性接著用組成物及所製成的溶液具有良好的耐熱性及耐化性等性質，以下特別作此實驗例。 薄膜的製備
依據下方表1所列出的本發明暫時性接著用組成物的配方比例（其中包含實施例1、實施例2及實施例3），於室溫下，將二酐單體、吸光單體、吸光材料及溶劑攪拌一小時，之後以約1 μm的厚度塗佈在700 μm的玻璃上，再放入烘箱中以160℃烘烤2分鐘，令表面乾燥，之後再以350℃烘烤半小時，如此可以得到暫時放置在玻璃表面上的暫時性接著用組成物薄膜(A)。當從玻璃取下後，可獲得本發明的暫時性接著用組成物薄膜(B)，厚度約1 μm。 表 1
實施例 1 實施例 2 實施例 3
OPDA 15wt% 15 wt% 15 wt%
DPDA 20 wt% 10 wt% 0
TPDA 0 10 wt% 20 wt%
碳黑 30 wt% 35 wt% 40 wt%
二氧化矽 15 wt% 10 wt% 5 wt%
NMP 20 wt% 20 wt% 20 wt%
鍍鈦銅測試
使用表1中實施例1的配方比例製成的薄膜(A)，於薄膜(A)上設置Ti/Cu層（Ti/Cu的厚度分別為100 nm/200 nm）。經鍍鈦銅測試，可得知鍍鈦銅膜面正常無龜裂，再於溫度230℃下進行2小時的高溫熟化，依然無裂痕。 熱裂解溫度
使用表1中實施例1的配方比例製成的薄膜(B)，藉由熱重分析儀(thermogravimetric analyzer，TGA)，量測薄膜(B)於損失5重量%時的溫度作為熱裂解溫度，量測出的熱裂解溫度為410℃，符合大於300℃的需求。 耐 TMAH 測試
使用表1中實施例1的配方比例製成的薄膜(A)，將2.38 %氫氧化四甲基銨（Tetramethylammonium Hydroxide，TMAH）在不同溫度下與薄膜(A)反應不同時間，測量重量損失百分比以評估耐化性，量測結果如下方表2所示。 表 2
反應時間 反應溫度
26℃ 50℃ 80℃
10分鐘 0.2% 1.1% 3.2%
20分鐘 0.1% 2.4% 5.8%
30分鐘 0.2% 5.2% 7.5%
耐化性測試 ( 使用實施1，薄膜(A))
使用表1中實施例1的配方比例製成的薄膜(A)，將薄膜(A)以下方表3中所列出的不同化學藥劑浸泡10分鐘，再以拉力計進行測量，當測量結果高於550 g/cm時，則代表具有良好的耐化性。量測結果如下方表3所示，可得知本發明的暫時性接著用溶液製成的暫時性接著層在浸泡於各種不同化學藥劑後，表現出良好的耐化性，即使是在浸泡常用於溶劑解黏的PGMEA後，仍具有高耐化性，因此，本發明的暫時性接著用組成物可克服習知技術中基於耐溶劑性不佳所導致的製程限制，更貼近市場需求。 表 3
化學藥劑 量測結果 (g/cm)
NMP 552
30% HCl 563
10% NaOH 550
PGMEA 570
甲醇 585
丙酮 577
解黏測試
使用表1中實施例1、實施例2以及實施例3的配方比例分別製成的薄膜(A)，以不同功率的波長為1064 nm的雷射光照射以進行解黏，評估結果如下方表4所示，其中O表示解黏開孔面積80 μm至100 μm，△表示解黏開孔面積50 μm至80 μm，X表示解黏開孔面積0 μm至50 μm。 表 4
功率 實施例 1 實施例 2 實施例 3
18W O O O
16W O O O
12W O O O
9W O O O
5W X △ O
3W X X △
密著性及剝離強度測試
使用表1中實施例1、實施例2以及實施例3的配方比例分別製成的薄膜(A)，密著性的評估方法採用百格密著性測試，測試方法是用百格刀在測試樣本（玻璃材料）表面劃10×10個(100個)1 mm×1 mm小網格，每一條劃線深及底層。之後，用毛刷將測試區域的碎片刷乾淨，再用膠紙牢牢黏住被測試小網格，並用橡皮擦用力擦拭膠帶，以加大膠帶與被測區域的接觸面積及力度。接著，用手抓住膠帶一端，在垂直方向迅速扯下膠紙。評估結果如下方表5所示，其中測試結果為5B即代表具有良好密著性。此外，表5中亦列出剝離強度的測試結果。 表 5
實施例 1 實施例 2 實施例 3
百格密著性測試 5B 5B 5B
剝離強度(g/cm) 430 525 480
穿透度測試
使用表1中實施例1、實施例2以及實施例3的配方比例分別製成的薄膜(A)，將薄膜(A)放置於全光譜分析儀中測試，其中薄膜(A)具有不同厚度。下方表6列出穿透度測試的評估結果（532 nm T.T）。 表 6
實施例 1 實施例 2 實施例 3
0.5 10% 8% 5%
1 5% 2.8% 1%
1.5 3% 2.4% 0%
2 2.6% 1% 0%
綜上所述，本發明的暫時性接著用組成物包含耐熱性高的二酐單體（OPDA）以具有良好耐熱性及密著性，同時含有吸光單體（DPDA及TPDA）以提升雷射光波長吸收度，更含有吸光材料（碳黑及二氧化矽）以吸收並折射光線，使得本發明的暫時性接著用組成物可藉由吸收波長為1064 nm的雷射光降低黏著力，具有容易解黏的特性。相較於習知的雷射解黏技術僅能於在波長為355 nm或532 nm的雷射光照射下解黏，本發明能夠使用紅光雷射解黏，故更具有優勢。此外，本發明的暫時性接著用組成物更具有良好耐熱性、耐化性及密著性，可解決習知UV光照射解黏及溶劑解黏技術之耐熱性及耐溶劑性不佳的問題，以克服製程上限制，更貼近市場需求。
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。
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Claims (8)

  1. 一種暫時性接著用組成物，包括：二酐單體；吸光單體，包括N,N,N,N-(對氨基苯基)-對苯二胺(DPDA)及N,N-(對氨基苯基)-對苯二胺(TPDA)中的至少一者；以及吸光材料，包括碳黑及二氧化矽，其中以所述暫時性接著用組成物的總重量計，所述二酐單體的添加量為10wt%至40wt%，所述吸光單體的添加量為10wt%至20wt%，所述吸光材料的添加量為20wt%至50wt%。
  2. 如申請專利範圍第1項所述的暫時性接著用組成物，其中所述二酐單體為2,3,3',4'-二苯醚四甲酸二酐(PDMS)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)以及3,3',4,4'-二苯醚四羧酸二酐(OPDA)的其中一種。
  3. 如申請專利範圍第1項所述的暫時性接著用組成物，更包括溶劑，所述溶劑包括N-甲基吡咯烷酮(NMP)、二甲基乙醯胺(DMAC)或環己酮。
  4. 如申請專利範圍第3項所述的暫時性接著用組成物，其中以所述暫時性接著用組成物的總重量計，所述溶劑的添加量為10wt%至60wt%。
  5. 如申請專利範圍第1項所述的暫時性接著用組成物，其中所述暫時性接著用組成物在波長為1064nm的雷射光照射下失去黏著力。
  6. 如申請專利範圍第1項所述的暫時性接著用組成物，其中所述暫時性接著用組成物的耐熱溫度為350℃至450℃。
  7. 一種暫時性接著用溶液，包括如申請專利範圍第1項至第6項中任一項所述的暫時性接著用組成物。
  8. 如申請專利範圍第7項所述的暫時性接著用溶液，其中以溶劑稀釋所述暫時性接著用組成物以製備所述暫時性接著用溶液，稀釋比例為10%至60%。
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