軟性混合電子元件製造的新結構性塑膠

作者 : Tony D. Flaim、Jennifer See,Brewer Science

已有令人驚訝的小範圍聚合物材料,能滿足微電子領域多年的結構性塑膠需求。

已有令人驚訝的小範圍聚合物材料,能滿足微電子領域多年的結構性塑膠需求。常見的名單包括環氧樹脂(填充和未填充)、聚亞胺、有機矽、BCB和BT樹脂。在很大的程度上會選擇這些聚合物化學物質,以與矽的剛性和低熱膨脹特性及傳統封裝製造中常用的高加工溫度搭配。然而,主要透過低溫添加劑加工技術製造的軟性混合電子元件的出現,使塑膠封裝材料需要具有更大的柔韌性和伸長率,且在200℃以上或最好是在150℃以上的溫度時,不需要太長的固化時間。

塑膠的基本種類

聚合物材料可分為兩大類,熱塑性塑膠和可固化塑膠,它們具有非常不同的分子結構。熱塑性聚合物材料主要由長的、無分支鏈的分子鏈組成,這些分子鏈盤繞且實際上糾結在一起,但在分子鏈之間沒有永久的化學鍵聯,即交聯。因此,熱塑性塑膠可以逆轉軟化,方法是將其加熱到一個溫度,在該溫度下,鏈內有足夠的鏈段運動,使其能在剪切力的作用下流動。

此行為是便捷的熱成型過程的基礎,例如熱熔擠出和射出成型。無交聯結構和典型高聚合物分子量的熱塑性塑膠可帶來許多所需要的性質,例如良好的機械強度、延展性、伸長率和韌性。另一方面,黏性聚合物鏈可能不容易與接觸表面相容,故當熱塑性塑膠塗覆或黏合到另一種材料上時,會導致較差的黏合性。同時,缺少交聯會使塑膠容易受到有機加工溶劑的侵蝕,例如當溶液在熱塑性基材上塗覆形成另一個塗層時。同樣的,熱塑性塑膠的可逆軟化特性,可能不利於高溫製程。

第二類主要的聚合物材料是可固化塑膠,是用於半導體封裝的主要形式。這些材料通常以低分子量樹脂的形式施加和加工,當以≥200℃加熱固化時,其會反應而形成多分支的超高分子量網路。緊密交聯的結構導致高勁度和剛性,以及強健的熱穩定性。

可固化塑膠因其對其他材料的出色黏合性而聞名,環氧樹脂就是一個有力的證明。但一如預期的是,大多數的可固化塑膠展現出極低的伸長率、可能很脆而且在重複的熱循環下容易開裂,使其不太適合軟性電子元件應用。

新型聚合物材料——PCT

Brewer Science設想出一種新的聚合物材料,其結合了所需要的熱塑性塑膠和可固化塑膠特性,以更好地實現軟性混合電路的生產。在我們的概念中,聚合物材料像熱塑性塑膠一樣提供高強度、伸長率和韌性,且能像可固化塑膠一樣提供高化學耐受性和熱流耐受性。更具體地說,Brewer Science開發出新的光固化熱塑性塑膠(PCT),其可在塗覆和成型後曝露於紫外線(UV)下形成交聯,新PCT材料的整體設計目標包含以下內容:

·高聚合物分子量具有適度的後固化交聯密度,以保持良好的機械強度、可撓性和韌性;

·本身具有光敏性,無需光酸產生劑、光引發劑、增效劑、交聯劑等添加劑;

·使用適合晶圓廠的溶劑成分,進行塗覆和澆膜;

·對半導體材料和其他塑膠有很強的黏著力;

·在光固化之前,能夠在200℃以下進行熱成型(模塑、壓印、擠出等);

·在300℃以上時保持熱穩定性;

·高脈衝UV雷射敏感度,便於快速、乾淨的雷射鑽孔。

可在施加和最終成型後對熱塑性材料進行光固化的能力,讓使用者能在固化前先利用其可逆轉的軟化特性,再經由固化將材料轉化為抗流狀態。與熱固化相反,使用光固化的能力可避免因同時發生的熱誘發軟化和交聯之間的競爭,而造成狹小的加工範圍。

PCT材料與性質

三種新的PCT組合物實例,可證明其獨特的化學、機械、熱和加工性質組合。新的聚合物組合物在此稱為PCT 1、PCT 2和PCT 3。其玻璃化轉變溫度(Tg)和分子量(MW)特徵列於表1中。透過固體聚合物樣品的差示掃描量熱分析法測定Tg值,同時借助凝膠滲透色譜法(相對於聚苯乙烯標準)測定所製備聚合物溶液的分子量性質。

20191212TA31P1-1
表1 新PCT聚合物的分子量特徵和玻璃化轉變溫度。

PCT材料的熱穩定性

組合物PCT 1的梯度熱重量分析(TGA)掃描影像如圖1所示。該材料顯示出優異的穩定性,直到超過360℃才發生重量損失。組合物PCT 2表現相似,展現出348℃的瞬間分解溫度。

20191212TA31P1
圖1 組合物PCT 1在氮氣下速度為10℃/分時的梯度TGA掃描。

PCT材料光固化前後的機械性質

處於預固化狀態的PCT聚合物是真正的熱塑性塑膠,且具有良好的可撓性和強度。表2所示的組合物PCT 1和PCT 2薄膜的機械性質資料,顯示其在室溫下為玻璃狀且中等硬度的材料。但其具軟性,且可以反覆彎曲而不會破斷。請注意,所示為在降伏點而非破斷點時的拉伸應力值。推測在破斷點時的拉伸應力即抗拉強度會更高。分別藉由動態機械分析(DMA)和熱機械分析(TMA)決定機械性質和熱膨脹係數(CTE)。

20191212TA31P1-2
表2 鑄態PCT薄膜的室溫機械性質(無光固化)。

透過光固化將化學交聯引入PCT膜有利於提高化學耐受性和減少熱流(參見後續章節)。但其不會引起脆化,而是會在猛烈彎曲時提高韌性和抗裂性。組合物PCT 1的薄膜仍非常柔韌,且在650瓦的實驗室UV燈下光固化5分鐘後仍可縐摺和折疊。

PCT材料的黏著性質

PCT聚合物顯示出對許多材料(包括其他聚合物)的黏著性。例如,將組合物PCT 1的溶液旋轉塗佈在矽和玻璃晶片上,再置於高溫板上以120℃烘烤10分鐘,隨後在烘箱中以130℃烘烤30分鐘,去除溶劑並留下乾燥的薄膜。再使用最高黏著強度的3M測試帶,對有刻痕的薄膜進行標準交叉陰影帶拉伸測試。圖2中的測試基材影像,基材都沒有畫素特徵消除的情況,表示PCT材料對矽和玻璃具有優異的黏著性。

20191212TA31P2
圖2 組合物PCT 1塗覆在矽和玻璃基材上的交叉影線膠帶拉伸測試結果。

光固化對PCT材料溶劑溶解度和流動性的影響

由於聚合物結構內的光誘發交聯,曝露於中度UV下會大幅改變新PCT材料的溶解度和熔融流動性質。圖3a顯示用650瓦實驗室UV燈照射5分鐘之前和之後,組合物PCT 2薄膜樣品的影像。UV照射引起明顯的薄膜顏色變化,但於此同時,其變得完全不受二甲基亞(DMSO,一種強力聚合物溶劑)的侵蝕,而未固化(未照射)薄膜的樣品在置於相同溶劑中後不到1分鐘內溶解。在圖3b中的兩個樣品小瓶影像可清楚地辨別溶解度的根本變化,後續研究顯示,只需30秒的UV燈照射,即可觀察到類似的溶解度變化。

20191212TA31P3
圖3 a(左)照射前後組合物PCT 2的薄膜外觀。b(右)在DMSO中浸漬20分鐘後照射和未照射的薄膜材料。

光固化亦大幅改變了PCT材料的熱軟化性能。圖4中的影像顯示以100℃加熱30分鐘後,第三種組合物PCT 3照射和未照射膜帶的行為。組合物PCT 3具有接近室溫的Tg,且具有非常高的彈性和伸長率,是柔軟的材料。當一條膜帶曝露在實驗室UV燈下幾分鐘後,將其折疊使膜帶末端與膜帶的中心部分接觸後再加熱時,接觸的區域不會流動且會黏合在一起,因其為透過曝光過程交聯。另一方面,未曝光膜帶的接觸區域容易流動並黏合在一起,基本上變成固體狀態。

20191212TA31P4
圖4 以100℃加熱30分鐘後,組合物PCT 3 UV照射和未照射膜帶的外觀。

PCT材料壓印

為證明PCT材料可以200℃以下熱成型,將已旋轉塗佈到200mm晶片上厚度5.8μm的未固化組合物PCT 2薄膜壓在第二個矽晶片上形成的聚矽氧烷壓模上,產生壓紋。壓製步驟以標準晶片接合工具(EVGroup Model 510)進行,晶片在4000N的作用力下加熱至170℃,持續5分鐘(壓力=~18.5psi)。再將組件冷卻至室溫,並以機械方式將壓模從壓印薄膜上剝離,PCT薄膜中壓印特徵的顯微影像如圖5所示。

20191212TA31P5
圖5 在170℃下在薄膜組合物PCT 2壓印圓圈和線條特徵的顯微影像。顯微照片中的數字為特徵尺寸,以μm為單位。

假設對壓紋進行光固化可使其穩定,而不會在加熱至高溫時回流。將一個壓印的晶片基材遮蓋一半,一面以實驗室UV燈照射5分鐘,而另一面未照射。當將晶片加熱至180℃並持續5分鐘後,光固化側的特徵完整保存,而未固化側的特徵有流動且變得不明顯,如圖6a和b中的對比顯微照片所示。

20191212TA31P6
圖6 a(左)光固化後加熱至180℃的壓印特徵的顯微照片。b(右)相同的壓印特徵,但在加熱前未進行光固化。

PCT材料的光學性質

新的PCT材料設計上本身即有對中度UV的感光性。意即光固化涉及功能部位(functional moieties)在聚合物結構內的直接反應,且不需要添加任何類型的光引發劑或增效劑,例如自由基固化的丙烯酸樹脂或陽離子固化的環氧塗料。這些相同的功能部位具有非常強的UV吸收力,表3所示組合物PCT 1中度UV波長的高光學消光係數(k)即為明證(k值為0.1的材料通常即視為具有高吸收力)。透過塗覆在矽晶片上聚合物薄膜的可變角度掃描橢圓偏光術,測定表2中的折射率和消光係數值。

20191212TA31P6-1
表3 PCT 1薄膜的折射率和光學消光係數。

PCT材料的雷射蝕刻

PCT材料在光譜上中UV光段的強吸光度,使其對通常在308355nm波長下工作的脈衝雷射蝕刻系統非常敏感。藉由使用以355nm操作的定製皮秒脈衝雷射系統,利用雷射光技術(Herman;MO),在矽晶片上塗覆一層1015μm厚的PCT 1近似變異體的焊盤(200×200μm)及通孔(100μm直徑)特徵圖案。其他相關的雷射操作參數如下:

·雷射脈衝能量:0.33μJ/脈衝;

·平均雷射功率:0.825mW;

·峰值雷射功率:22kW;

·脈衝長度:< 15ps;

·雷射重複率:2,500Hz。

圖7顯示在去離子水中經音波振動清潔幾分鐘後,樣品上焊盤和通孔特徵的顯微影像(PCT材料為黃綠色,而以雷射輕微蝕刻並照射後的矽,具有粗糙的金屬外觀)。可以看出,蝕刻過程產生很少的碳質殘留物,且特徵邊緣尖銳而鬆脆。值得注意的是,蝕刻是在< 1mW的平均雷射功率下進行,更高的功率設置會導致PCT材料焦化,因其能非常有效地吸收雷射光。

20191212TA31P7
圖7 利用皮秒雷射蝕刻系統,在與PCT 1密切相關的結構變異體中形成之焊盤和通孔特徵圖案的顯微影像。

PCT材料總結和潛在應用

光固化熱塑性聚合物代表結構性塑膠的新設計典範。其將高分子量熱塑性塑膠的理想機械性質與可固化塑膠的耐熱性和化學耐受性相結合。此外,人們可以利用傳統加工流程中材料的熱塑性和可固化特性,因為起始熱塑成型的固化仰賴UV輻照,而非可固化塑膠通常需要的加熱至高溫。

可預見PCT材料的強大物理特性和獨特的加工可能性,在各種軟性混合電路應用中的價值。顯然,其良好的可撓性和伸長率,以及遠高於室溫的良好剛度,表示可將其作為基礎基底材料。也許更有趣的是,可以想像一種基材,其中有以圖案光固化形成的較剛性區域,以及留在熱塑性(未固化)狀態的較軟性區域。不難想像這些新材料的其他用途,本文向讀者發出挑戰,思考如何在微電子應用中使用PCT材料。

本文同步刊登於EE Times Taiwan 12月號雜誌

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