TWI492303B - 增進光及／或雷射燒結之緩衝層 - Google Patents

增進光及／或雷射燒結之緩衝層 Download PDF

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TWI492303B
TWI492303B TW099109236A TW99109236A TWI492303B TW I492303 B TWI492303 B TW I492303B TW 099109236 A TW099109236 A TW 099109236A TW 99109236 A TW99109236 A TW 99109236A TW I492303 B TWI492303 B TW I492303B
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thermal conductivity
substrate
low thermal
photo
polyimine
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TW201106426A (en
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Zvi Yaniv
Mohshi Yang
Peter B Laxton
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Applied Nanotech Holdings Inc
Ishihara Chemical Co Ltd
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Description

增進光及/或雷射燒結之緩衝層
本案主張美國臨時專利申請案序號61/174,758及61/163,894之優先權。
本發明關於一種在基材上沈積導電性線路的方法以及電子電路。
微電子學及半導體封裝工業已開始轉移至可印刷之電子學。電子電路包含各種彼此電連接之組件。該等介於不同組件之間的電連接可由可使用導電性墨液印刷於基材上之導電性金屬跡線(trace)作成。該等墨液在沈積於基材上之後加以處理及燒結，以變成導電性。熱燒結使用高溫(例如，250℃)將墨液中之奈米粒子熔融。光子(光)及雷射燒結採用極高強度之燈/雷射而於極短時間中(例如微秒)以低溫熔融該等奈米粒子，因而不傷害底層基材。然而，該光/雷射燒結方法存有極限，基材需使用低熱導係數材料，以便在熱能消散至基材之前，奈米粒子能有效吸收能量並燒結。換言之，可使用於該等應用中之基材會極受限於低熱導係數材料。
另一方面，低熱導性基材可用於撓性可印刷電子裝置。低溫熔點材料，諸如聚乙烯(PE)、聚酯(PET)等，會防礙奈米粒子墨液進行適當之燒結，且該等基材會受損，結果為電阻係數極高。
1.　光燒結製程之效能不僅取決於金屬奈米粒子尺寸，亦取決於物質種類。
2.　有效光燒結係由小於300 nm之奈米粒子達成。
3.　基材之熱導係數會影響金屬墨液光燒結。基材熱導係數愈底，奈米粒子薄膜之導電性愈佳。
4.　高熱導性基材可藉由塗覆低熱導係數材料諸如聚醯亞胺或聚合物加以調整及隔離，以進行有效之光燒結製程。
5.　隔離熱耗散所需之聚醯亞胺厚度約為1至50微米。
6.　變成導電性薄膜之銅墨液已於高熱導性材料(諸如矽晶圓)上使用雷射及光繞結兩者皆得到證明。
7.　高熱導性矽晶圓之熱耗散已使用塗覆於晶圓上之各種聚醯亞胺厚度予以證明。可將低熱導性材料用作緩衝層，以減緩熱耗散且增進光或雷射燒結。
8.　銅墨液可在矽晶圓上塗覆聚醯亞胺之情況下充分燒結，光燒結之電阻係數為1×10-5 歐姆-厘米且雷射燒結為4×10-6 歐姆-厘米。
9.　聚醯亞胺材料不僅可用作在高熱導性基材上之絕熱體，並增進銅墨液光及雷射燒結效能，且亦可施加於低熔點基材上作為絕熱體，以在燒結製程中保護該基材防止熱損傷。
10.聚醯亞胺層及金屬跡線層可重複數次成為多層電路。
11.聚醯亞胺層可用作介電材料且合倂為電容器。
12.可於頂層導體上使用奈米-銅墨液作為二維及三維晶片封裝應用中之接觸金屬。
本發明具體實施態樣揭示一種光燒結法，其有效地燒結位於聚醯亞胺基材上之金屬奈米粒子，因而造成接近本體材料之薄膜極具導電性。另一方面，光燒結方法並非極適於塗覆在具有高熱導係數之基材(諸如陶瓷及矽晶圓)上的奈米粒子墨液。表1顯示各種材料之熱導係數。
低熱導係數材料，諸如聚醯亞胺，可於其他高熱導係數基材(諸如陶瓷及矽晶圓)上用作塗覆材料，以隔絕在光燒結過程中奈米粒子之熱能耗散，而使奈米粒子更有效率地熔融。熱耗散之快慢取決於低熱導係數材料(例如，聚醯亞胺薄膜)之厚度。
進行以下實驗以顯示本發明的操作方式。於三片晶圓各別旋塗1、1.5及2.3微米厚之DuPont PI-2610聚醯亞胺，在350℃下熱固化30分鐘。使用一片裸矽晶圓作為參考物(晶圓#1)。全部四片晶圓皆使用洩降(drawdown)程序塗覆銅墨液。於100℃乾燥程序60分鐘後，每片晶圓各分成三區，每一區各以三種不同能階獨立燒結。使用伏特計(voltmeter)測量每一區及每片晶圓之電阻，結果示於表2中，顯示在矽晶圓上光燒結各種不同塗層厚度之聚醯亞胺後的銅膜電阻。
其中　能量1=3次850/1050 V燒結射注，1000 μsec
能量2=4次850/1150 V燒結射注，1000 μsec
能量3=5次850/1250 V燒結射注，2000 μsec
除晶圓4之第3區外，四片晶圓之所有區在光燒結後皆無電阻改變。晶圓4第3區在最高能階下經歷其金屬顏色改變，如圖1所示。該區域被嚴重吹離。周圍區域留有導電性銅碎屑。此係該聚醯亞胺材料可用為絕熱體之明證。聚醯亞胺厚度可大於3微米。聚醯亞胺及矽之熱導係數各為0.12及148 W/m.K。由於無聚醯亞胺材料，故熱太快耗散至矽基材(晶圓#1)內而無法使銅奈米粒子燒結。
晶圓1、2及3皆具有高值電阻(大於20百萬歐姆)。圖1所示具有20歐姆電阻之晶圓4中心區顯示銅奈米粒子薄膜開始熔融、燒結且轉化成銅顏色。因此可使用較厚低熱導係數材料作為良好絕熱體。
除了前文所揭示之液體聚醯亞胺之外，亦採用乾燥聚醯亞胺膜。將銅墨液塗覆於50微米聚醯亞胺膜(Kapton)上。將該試樣置於矽晶圓及carbAL高熱導性散熱器上，如圖2所示。將矽滑脂塗覆於Kapton及矽晶圓與carbAL之間，以確保良好之熱接觸。將該試樣以單一射注同時予以光燒結。銅係極充分地燒結，轉變成閃亮銅色，如圖3所示。Kapton之下的材料並不重要。至少50微米厚的聚醯亞胺即厚至足以隔離且預防光燒結製程之熱能耗散，但在導電性跡線期望較低電導係數之具體實施態樣中亦可採用小於50微米之厚度。
此外，在矽晶圓上使用設定如同前述之雷射燒結設置。該雷射係為波長830 nm且功率800 mW之固態二極體。聚焦波束尺寸為直徑15微米且藉由準直儀及接物鏡控制，如圖4及5所示。
此雷射具有足以燒結且熔融奈米粒子且使銅墨液成為導電性之功率。有四片各塗覆1、1.5、2及3微米之各種聚醯亞胺厚度的矽晶圓，還有作為參考物之裸矽晶圓。每一晶圓之電阻係數各以雷射功率繪於圖6，顯示銅膜電導係數係與聚醯亞胺厚度成比例，且雷射所產生之熱在存有聚醯亞胺之情況下的傳送少於不具有聚醯亞胺之裸矽晶圓。此點明確證實任何具有低熱導係數之材料--諸如聚醯亞胺材料--皆可用作絕熱體而增進光及雷射燒結製程。
此外，在矽晶圓上塗覆各種聚醯亞胺厚度，並在350℃固化一小時。隨後藉洩降塗覆標準銅墨液，於爐中乾燥，且以光/雷射燒結。進行電測量且測定銅墨液試樣之特性。
使用DuPont製造之三種聚醯亞胺材料在1000、2000、3000、4000及5000 rpm下旋塗於矽晶圓上。圖7說明顯示在各種轉速下測量之固化聚醯亞胺厚度的圖。在每一晶圓上之範圍各為1至20微米。
製備試樣之後，於銅墨液上進行光及雷射燒結。針對電阻係數及黏著性，以及雷射燒結之線寬，比較不同類型之燒結。表3顯示在各種聚醯亞胺厚度下於相同能階光燒結之試樣。表4顯示在各種聚醯亞胺厚度下於固定功率位準雷射燒結之試樣。
圖8說明顯示燒結銅膜之電阻係數與聚醯亞胺厚度成反比的圖。光燒結之電阻係數飽和點約為10微米，雷射燒結約為5微米。光燒結之功率密度遠低於雷射燒結，提供其電阻係數較高之原因。
圖9說明顯示銅墨液薄膜對聚醯亞胺之黏著性與聚醯亞胺厚度成比例的圖。雖存有某些雜訊點，但圖中趨勢明確。聚醯亞胺愈厚，黏著性愈佳。同樣的，光燒結之良好黏著性聚醯亞胺厚度臨界點約為10微米，而雷射燒結約為5微米。
圖10說明顯示雷射寫入線寬度與雷射功率密度成比例的圖。在已知雷射功率下，雷射寫入線寬亦與聚醯亞胺薄膜厚度成比例，為聚醯亞胺對此等製程係良好絕熱體提供更多證據。在聚醯亞胺厚度增加時，沈積於銅墨液表面上之雷射能量及熱在垂直方向無法展布得更深，側向除外。
參考圖11A至11F，說明執行本發明具體實施態樣之程序。提供表面待裝配電子電路之基材1101。於圖11B中，使用眾所周知之製造程序於基材1101上依所需圖案沈積金屬材料跡線1102。圖11C中，將低熱導係數材料1103諸如聚醯亞胺之層塗覆於金屬跡線1102及基材1101上。為生成待沈積導電性跡線的其他圖案，形成貫穿材料1103之通孔1104，暴露出金屬跡線1102之某些部分。在圖11E中，墨液噴射裝置1106在材料1103及由通孔1104暴露之金屬跡線1102上沈積導電性墨液1105，諸如銅奈米粒子。在圖11F中，於所沈積之導電性墨液奈米粒子1105上進行光或雷射燒結程序，將其燒結成導電性跡線1107，如本文所述。沈積導電性墨液及燒結程序係描述於美國專利公開案2008/0286488 A1中，該案係以引用方式倂入本文。
1,2,3,4．．．晶圓
1101．．．基材
1102．．．金屬跡線
1103．．．低熱導係數材料層
1104．．．通孔
1105．．．導電性墨液
1106．．．墨液噴射裝置
1107．．．導電性跡線
圖1係為數位相片，顯示光燒結於四個矽晶圓上之銅墨液。
圖2係為數位相片，顯示光燒結之前的銅墨液。
圖3係為數位相片，顯示光燒結之後的銅墨液。
圖4係為數位相片，顯示在Kapton基材上之雷射燒結線路。
圖5係為放大之數位相片，顯示圖4之雷射燒結線。
圖6說明顯示藉雷射燒結之銅墨液電阻係數不僅與雷射能量成反比，亦與由聚醯亞胺製得之緩衝層厚度成反比的圖。
圖7說明顯示在各種轉速下測量之固化聚醯亞胺厚度的圖。
圖8說明顯示燒結銅膜之電阻係數與聚醯亞胺厚度成反比的圖。
圖9說明顯示銅墨液薄膜對聚醯亞胺之黏著性與聚醯亞胺厚度成比例的圖。
圖10說明顯示雷射寫入線寬度與雷射功率密度成比例的圖。
圖11A至11F說明本發明具體實施態樣之方法。
1101．．．基材
1102．．．金屬跡線
1103．．．低熱導係數材料層
1107．．．導電性跡線

Claims (25)

  1. 一種於基材上沈積導電性線路的方法，其包含：於該基材上塗覆具有低熱導係數之材料層；在該具有低熱導係數之材料層上沈積導電性墨液薄膜；及光燒結該導電性墨液之薄膜。
  2. 如申請專利範圍第1項之方法，其進一步包含：於該基材上依圖案沈積金屬層，其中該具有低熱導係數之材料層係塗覆在該經圖案化之金屬層及該基材上；形成貫穿該具有低熱導係數之材料層的通孔以暴露一部分經圖案化之金屬層，其中導電性墨液薄膜之沈積係包括將導電性墨液薄膜沈積至該通孔內，以將導電性墨液薄膜塗覆經圖案化金屬層之部分，其中塗覆該經圖案化金屬層之部分的導電性墨液薄膜亦被光燒結。
  3. 如申請專利範圍第2項之方法，其中塗覆於該經圖案化金屬層部分上的導電性墨液薄膜所耗散來自光燒結之能量沒有塗覆於具有低熱導係數之材料層上之導電性墨液薄膜那麼多。
  4. 如申請專利範圍第3項之方法，其中該具有低熱導係數之材料層包含聚合物。
  5. 如申請專利範圍第3項之方法，其中該具有低熱導係數之材料層包含聚醯亞胺。
  6. 如申請專利範圍第5項之方法，其中該聚醯亞胺具有至少50微米的厚度。
  7. 如申請專利範圍第5項之方法，其中該光燒結係以光燒結裝置進行。
  8. 如申請專利範圍第5項之方法，其中該光燒結係以雷射燒結裝置進行。
  9. 如申請專利範圍第8項之方法，其中該雷射燒結裝置包含具有830nm波長及800mW功率之固態二極體。
  10. 如申請專利範圍第9項之方法，其中該固態二極體具有直徑為15微米的聚焦波束尺寸。
  11. 如申請專利範圍第5項之方法，其中該聚醯亞胺具有至少5微米的厚度。
  12. 如申請專利範圍第5項之方法，其中該聚醯亞胺具有至少2.3微米的厚度。
  13. 如申請專利範圍第5項之方法，其中該基材包含矽。
  14. 如申請專利範圍第5項之方法，其中該基材包含陶瓷。
  15. 如申請專利範圍第1項之方法，其中該基材具有大於該具有低熱導係數之材料層的熱導係數。
  16. 如申請專利範圍第5項之方法，其中該導電性墨液之薄膜包含銅奈米粒子。
  17. 一種電子電路，其包含：基材；塗覆於該基材上之低熱導性材料層；及在該塗覆於基材上之低熱導性材料層上所塗覆的光燒 結導電性墨液薄膜。
  18. 如申請專利範圍第17項之電子電路，其中該基材具有大於該低熱導性材料層之熱導係數。
  19. 如申請專利範圍第18項之電子電路，其中該低熱導性材料層包含聚醯亞胺。
  20. 如申請專利範圍第19項之電子電路，其中該聚醯亞胺具有至少50微米之厚度。
  21. 如申請專利範圍第19項之電子電路，其中該光燒結導電性墨液包含以光燒結裝置光燒結之光燒結銅奈米粒子。
  22. 如申請專利範圍第19項之電子電路，其中該光燒結導電性墨液包含以雷射燒結裝置光燒結之光燒結銅奈米粒子。
  23. 如申請專利範圍第19項之電子電路，其中該聚醯亞胺具有至少5微米之厚度。
  24. 如申請專利範圍第19項之電子電路，其中該聚醯亞胺具有至少2.3微米之厚度。
  25. 如申請專利範圍第19項之電子電路，其中該基材包含矽。
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US8647979B2 (en) 2014-02-11
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