TW201621091A - 具有大晶粒之銅薄膜、包含其之銅箔基板、以及該銅箔基板之製備方法 - Google Patents

具有大晶粒之銅薄膜、包含其之銅箔基板、以及該銅箔基板之製備方法 Download PDF

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TW201621091A
TW201621091A TW103143343A TW103143343A TW201621091A TW 201621091 A TW201621091 A TW 201621091A TW 103143343 A TW103143343 A TW 103143343A TW 103143343 A TW103143343 A TW 103143343A TW 201621091 A TW201621091 A TW 201621091A
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copper
copper film
film
substrate
crystal
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陳智
呂佳凌
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國立交通大學
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Abstract

本發明提供一種具有大晶粒之銅薄膜，其中在該銅薄膜之至少一表面上，50%以上之面積的晶粒係沿[100]晶軸方向成長，且該複數個晶粒的平均大小為150 mm以上。本發明之銅薄膜上的晶粒尺寸較大，且具有高度優選的方向性，因此可使銅薄膜具有良好的可撓性、穩定度以及抗電遷移特性。本發明亦提供具有上述銅薄膜之銅箔基板。

Description

具有大晶粒之銅薄膜、包含其之銅箔基板、以及該銅箔基板之製備方法
本發明係有關於一種銅薄膜、包含其之銅箔基板、以及該銅箔基板之製備方法，特別的是，有關於一種具有大晶粒之銅薄膜、包含其之銅箔基板、以及該銅箔基板之製備方法。
隨著科技的演進，對於電子產品的訴求已偏向輕薄短小以及具備良好的可撓性質為市場趨勢。在相關製程中常大量使用銅材作為導體，為了因應市場需求，製造輕薄、以及具有良好的延展性與可撓性之軟性銅箔基板的技術成為目前研發的重點。
然而，在習知用於製造軟性銅箔基板的方法中，壓延銅箔雖可具有較佳的耐折曲性，然而其受限於厚度，無法製備過薄的銅箔，且成本較高，並不符合現今的發展趨勢；而電鍍銅箔雖然可製備為較薄，但其是採用電解方式形成，銅箔的內部結構組織呈現垂直柱狀，當彎曲時恐產生裂紋而發生斷裂，故可撓性不佳。因此，有需要發展製備具有良好延展性、薄型、低成本的銅箔基板的方法。
本發明提供一種具有大晶粒之銅薄膜、包含其之銅箔基板、以及該銅箔基板之製備方法，其中根據本發明之製備方法所提供之銅薄膜由於經過退火處理步驟，因此晶粒可重新形成，進而在結晶時使晶粒的大小增大、並且以高度優選方向成長，亦即，沿[100]晶軸方向成長。因此，可具較佳的延展性，且在撓曲時晶界所產生的裂紋小，亦具備優良的可撓性、良好的機械、光電、熱穩定性與抗電遷移特性，故可有利於製備尺寸輕薄的電子產品的應用。
根據本發明實施例，提供一種具有大晶粒之銅薄膜，其中在該銅薄膜之該至少一表面上，50%以上之面積的複數個晶粒係沿[100]晶軸方向成長，且該複數個晶粒的平均大小為150 μm以上。
根據本發明之另一實施例，提供一種銅箔基板，其包含：基板；以及上述具有大晶粒之銅薄膜設置於該基板上。
根據本發明之又一實施例，提供一種銅箔基板之製備方法，其包含：於基板之表面上電鍍成長銅箔晶粒以獲得[111]奈米雙晶銅薄膜；以及將[111]奈米雙晶銅薄膜於200~500℃之溫度下進行退火處理以獲得具有大晶粒之銅薄膜，其中在該銅薄膜之該至少一表面上，具有50%以上沿[100]晶軸方向成長之複數個晶粒。
以下藉由具體實施例配合所附的圖式詳加說明，當更容易瞭解本發明之目的、技術內容、特點及其所達成之功效。
本發明將藉由下述之較佳實施例及其配合之圖式，做進一步之詳細說明。需注意的是，以下各實施例所揭示之實驗數據，係為便於解釋本案技術特徵，並非用以限制其可實施之態樣。
一般來說，材料內部的晶粒及其組織對於性能有很重要的影響，當晶粒的尺寸越大，晶界越少，可大幅降低當材料被撓曲時晶界所產生的裂痕，故可具備良好的可撓性優勢。因此，在本發明之一實施例中，提供一種具有大晶粒之銅薄膜，其中，複數個晶粒是成長於銅薄膜之至少一表面上。至少一表面代表上表面及/或下表面。在銅薄膜之至少一表面上，50%以上之面積的複數個晶粒係沿[100]晶軸方向成長，較佳地，80%以上之面積的複數個晶粒係沿[100]晶軸方向成長，更佳地，90%以上之面積的複數個晶粒係沿[100]晶軸方向成長。
值得一提的是，於本實施例中，在垂直於銅薄膜的法向量之15度內皆定義為[100]晶軸方向。如圖1所示為垂直於銅薄膜的法向量之X軸15度內，但本發明並不以此為限。其中，複數個晶粒20成長於基板10的一表面上。於此，以晶粒20進行例示性的說明，然其並不意欲限制本發明中晶粒20與基板10之相對大小。
本發明之銅薄膜可具有大尺寸的複數個晶粒，且複數個晶粒的平均大小可為150 μm以上，較佳地，該複數個晶粒的平均大小可為400~700 μm。其中，銅薄膜10之厚度可為0.1~200 μm，較佳地，銅薄膜之厚度可為2~50 μm。另一方面，本發明之具有大晶粒之銅薄膜的彈性模數(Modulus)約為100~150 GPa，較佳地，約為133.6 GPa；而本發明之具有大晶粒之銅薄膜的硬度約為1~2 GPa，較佳地，約為1.68 GPa。
根據本發明之一實施例，提供一種銅箔基板之製備方法。本發明之銅箔基板之製備方法包含：於基板之表面上電鍍成長銅箔晶粒以獲得具有高密度且晶粒規則排列的[111]晶軸方向奈米雙晶銅薄膜，其可參照中華民國專利第I432613號中所述之方法，在此以參照方式將其引入本文。
在本發明之另一實施例中，用於電鍍之基板可為同質基板或異質基板。當基板為同質基板時，可直接電鍍成長銅薄膜晶粒於該基板上。而當基板為異質基板時，基板可為矽晶圓或其他合適的基材，但其並不以此為限制。而在電鍍步驟之前，更包含先在基板上濺鍍一接著層以電鍍成長銅薄膜銅箔晶粒於基板，且接著層之材料可包含但不限於為鈦鎢(TiW)。
在本發明之另一實施例中於基板或接著層上塗佈一銅晶種層，以有利於晶粒的成長。在一實施例中，可將200 nm厚之[111]銅濺鍍於其上以作為晶種層。此外亦可於電鍍成長銅薄膜晶粒於基板上後，再將該銅箔撕起，以得到其單一表面具有[100]晶粒之銅薄膜，藉此可不為退火溫度影響，因而改善製程溫度過高造成在印刷電路板工業之應用的限制。
以下通過具體實施例配合附圖詳加說明，可更容易瞭解本發明的目的、技術內容、特點及所達成的功效，並據以實施，但不能以此限定本發明的保護範圍。
接著，將根據一例示性實施例說明本發明之銅箔基板之製備方法，其相關詳細製程步驟已見於NPG Asia Materials(2014) 6,e135，在此以參照方式引入本文中。首先，利用脈衝電鍍法製備朝[111]晶軸方向排列之晶粒，其包含下列步驟：以高純度的硫酸銅(CuSO4 )溶液添加合適的表面活性劑以及40 p.p.m氯化氫(HCl)作為電解液、並以99.99%高純度銅片作為陰極，並使用矽晶圓作為基板，再濺鍍厚度為200 nm的鈦鎢(TiW)作為接著層，並接著使用Oerlikon ClusterLine 300 (OC Oerlikon Corporation AG, Pfäffikon, Switzerland)將200 nm厚的朝[111]銅濺鍍於接著層上以作為晶種層。
矽晶圓可被切割為3x1 cm2 或2x1 cm2 的片狀，且於脈衝電鍍時浸入電解液中。成長奈米雙晶銅的旋轉速率為600 r.p.m.，且電流密度為50 mA cm−2 。實驗週期為Ton =0.02 s，且Toff =1.5 s。沉積速率為1.2 nm s−1 。藉此，以獲得具有高密度且晶粒規則排列的[111]晶軸方向奈米雙晶銅薄膜。
接著，將沿著[111]晶軸方向堆疊之奈米雙晶銅薄膜置於真空退火爐內於200~500℃之溫度下進行退火處理產生再結晶以得到大尺寸[100]晶軸方向晶粒之銅薄膜，較佳地，可於250~450℃之溫度下進行退火處理約60分鐘。於此，於5×10−7 torr之石英管中進行退火處理。
在本實施例中，分別使用聚焦離子束(focused ion beam, FIB)以檢測銅膜的晶粒形狀、利用X-ray繞射分析銅膜的紋路分析、並且使用電子背向散射繞射(electron back-scattered diffraction, EBSD)檢驗各別晶粒於銅膜上的走向。其中，電子背向散射繞射分析是以EDAX/TSL系統於25 kV下操作JEOL 7001 F冷場發射掃描式電子顯微鏡(field-emission scanning electron microscope) (JEOL Ltd., Tokyo, Japan)而進行檢驗。
其結果如圖2a、2b、3a所示。參考圖2a，藉由上述方法進行電鍍可確實獲得皆朝[111]晶軸方向成長之表面晶粒，且晶粒平均大小約為2.38±0.85 μm。而如圖2b所示，根據X ray繞射結果顯示，銅膜均成長為高度的[111]方向。再參考圖3a，藉由上述退火處理，可發現上述朝[111]晶軸方向排列之晶粒經過以上退火處理後，係幾乎完全地轉變成長方向為[100]。
請參閱圖3b，該些晶粒的平均大小可為150 μm以上，較佳地，該些晶粒的平均大小可為400~700 μm。且所產生之大尺寸晶粒具有高度優選方向，在銅薄膜之至少一表面上，50%以上之面積的複數個晶粒係沿[100]晶軸方向成長，較佳地，80%以上之面積的複數個晶粒係沿[100]晶軸方向成長，更佳地，90%以上之面積的複數個晶粒係沿[100]晶軸方向成長。
綜合上述，根據本發明所揭露之製備方法，於傳統電鍍製程後進行退火處理，可使銅薄膜/箔的晶粒重新形成，在結晶使晶粒的尺寸增大且具有高度優選的方向性。因此，控制熱處理的溫度及時間可確保銅箔的晶粒大小和晶粒取向符合需求。而根據本發明之製備方法所獲得之銅薄膜具有大尺寸且具有高度優選的方向性之晶粒，具有優良的可撓折性、優秀的機械、電、光與熱的穩定度、以及抗電遷移特性，可有效地應用於相關產業的發展。
10‧‧‧基板
20‧‧‧晶粒
圖1為根據本發明實施例之晶粒成長方向示意圖。 圖2a及圖3a為晶粒的電子背向散射繞射(electron back-scattered diffraction, EBSD)分析示意圖。 圖2b為X ray繞射結果。 圖3b為根據本發明實施例之晶粒的直徑分析。
10‧‧‧基板
20‧‧‧晶粒

Claims (11)

  1. 一種具有大晶粒之銅薄膜，其中在該銅薄膜之該至少一表面上，50%以上之面積的複數個晶粒係沿[100]晶軸方向成長，以及該複數個晶粒的平均大小為150 mm以上。
  2. 如請求項1之具有大晶粒之銅薄膜，其中在該銅薄膜之該至少一表面上，80%以上之面積的該複數個晶粒係沿[100]晶軸方向成長。
  3. 如請求項1之具有大晶粒之銅薄膜，其中該銅薄膜之厚度為0.1~200 mm。
  4. 如請求項1之具有大晶粒之銅薄膜，其中該銅薄膜之厚度為2~50 mm。
  5. 如請求項1之具有大晶粒之銅薄膜，其中該複數個晶粒的平均大小為400~700 mm。
  6. 如請求項1之具有大晶粒之銅薄膜，其中該複數個晶粒成長於該銅薄膜之上下表面。
  7. 一種銅箔基板，其包含： 一基板；以及 如請求項1至請求項6之任一之有大晶粒之銅薄膜設置於該基板上。
  8. 如請求項7之銅箔基板，更包含： 一接著層，其設置於該銅薄膜及該基板之間。
  9. 如請求項8之銅箔基板，其中該接著層之材料為鈦鎢(TiW)。
  10. 如請求項7之銅箔基板，更包含一銅晶種層，其設置於該銅薄膜及該基板之間。
  11. 一種如請求項7至請求項10任一之銅箔基板之製備方法，其包含： 於一基板之一表面上電鍍成長銅箔晶粒以獲得一[111]奈米雙晶銅薄膜；以及 將該[111]奈米雙晶銅薄膜於200~500℃之溫度下進行退火處理以獲得具有大晶粒之一銅薄膜，其中該銅薄膜具有50%以上沿[100]晶軸方向成長之複數個晶粒。
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