應用於先進半導體封裝之液態高二氧化矽填充環氧樹脂封裝材料配方/性質研究

Abstract

本研究主要開發液態環氧樹脂封裝材料 (liquid epoxy molding compounds)，環氧樹脂封裝材料是藉由環氧樹脂 (epoxy resins)、固化劑 (hardeners)、催化劑 (accelerators)、增韌劑 (tougheners)、二氧化矽 (silica)及矽烷耦合劑 (silane coupling agents)等材料經過加熱交聯而成，並利用差示掃描量熱儀 (DSC)、動態機械分析儀 (DMA)、熱機械分析儀 (TMA)及三點彎曲試驗 (3PB)等進行性質測量。本研究分成兩個部分，第一部分為環氧樹脂配方研究，第二部分為二氧化矽複合材料配方研究。 第一部分為環氧樹脂配方研究，我們首先比較固化劑種類對系統性能的影響，並使用BE114、BFE283及NPEL-128三種環氧樹脂進行催化劑及增韌劑添加量對系統影響的研究。在固化劑種類實驗中，比較胺和酸酐兩種固化劑，通過DSC及DMA的測試，發現酸酐固化劑具有較適合的反應溫度和較高的玻璃轉移溫度(Tg)，因此我們選擇酸酐作為固化劑。接著，進行催化劑添加量實驗，DSC結果顯示隨著催化劑添加量增加，反應溫度下降；而DMA結果顯示Tg隨催化劑添加量增加有上升的趨勢。最後，進行增韌劑添加量實驗，由DSC結果發現隨著增韌劑添加量增加，反應溫度上升；而DMA結果發現Tg和儲存模數(E’)隨增韌劑添加量增加而下降。 第二部分為二氧化矽複合材料配方研究，我們選用BE114作為環氧樹脂基材，酸酐作為固化劑，0.75%作為催化劑的添加量，進行二氧化矽及矽烷耦合劑添加量對系統影響的研究。在二氧化矽添加量實驗中，DSC結果顯示隨著二氧化矽添加量增加，反應溫度上升，然而反應焓會下降且低於理論反應焓；DMA結果顯示隨著二氧化矽添加量增加，Tg會下降，而E’會上升；TMA結果顯示隨著二氧化矽添加量增加，α1及α2皆會下降，Tg也會下降，這與DMA的結果相同；3PB結果顯示增加二氧化矽含量會導致彎曲模數 (flexural modulus)上升，同時導致彎曲強度 (flexural strength)及斷裂應變 (break strain)下降。然而，增加增韌劑含量會導致彎曲模數及彎曲強度下降。在矽烷耦合劑添加量實驗中，DSC結果發現隨著矽烷耦合劑添加量增加，反應溫度下降；DMA結果發現隨著矽烷耦合劑添加量增加，Tg及高溫區的E’會下降，而低溫區的E’會上升；TGA結果發現加入矽烷耦合劑並不會影響在300°C的熱穩定性。綜上所述，本研究為液態環氧樹脂封裝材料的開發提供重要的資訊，並為相關研究領域奠定了基礎。

This study focuses on developing liquid epoxy molding compounds (EMCs). Epoxy molding compounds are formulated using a combination of epoxy resins, hardeners, accelerators, tougheners, silica, and silane coupling agents. Various characterization techniques such as differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermomechanical analysis (TMA), and three-point bending test (3PB) are utilized to measure the material properties of EMCs. The research is divided into two parts: the first part focuses on the formulation of epoxy resin, while the second part focuses on the formulation of silica composite materials. The first part of the study focuses on the formulation of epoxy resins. Initially, we compare the effects of various types of hardeners on the performance of the system. We conduct an investigation to study the influence of accelerator and toughener concentrations on the properties of three epoxy resins: BE114, BFE283, and NPEL-128. In order to compare the effects of different types of hardeners, including amines and anhydrides, we conduct DSC and DMA tests. The results indicate that anhydride hardeners require high curing temperatures and exhibit higher glass transition temperature (Tg) after curing. Consequently, we select anhydrides as the preferred hardeners for further investigations. Subsequently, we conduct experiments to study the effects of accelerator concentrations. DSC results show that as the accelerator concentration increases, the curing temperature decreases. The DMA results indicate an upward trend in Tg of the cured samples as the accelerator concentration increases. Finally, we examine the impact of toughener concentrations. The DSC results reveal that increasing the concentration of the toughener leads to an increase in curing temperature. The DMA results demonstrate that as the concentration of the toughener increases, both Tg and storage modulus (E’) decrease. The second part of the study focuses on the formulation of silica composite materials. BE114 is selected as the epoxy resin matrix, anhydride as the hardener, and an accelerator concentration of 0.75%. The study investigates the effects of silica and silane coupling agent concentrations on the thermal and mechanical properties of the composite systems. In the experiments involving varying silica concentrations, the results from DSC show that as the concentration of silica increases, the curing temperature increases. However, the enthalpy of the reaction decreases and is lower than the theoretical value. The DMA results indicate that as the silica concentration increases, Tg decreases while the E’ increases. The TMA results reveal that an increase in silica concentration leads to a decrease in both α1 and α2, resulting in a decrease in Tg, which is consistent with the DMA results. The results of the three-point bending test (3PB) show that an increase in silica content leads to an increase in flexural modulus, but a decrease in flexural strength and break strain. However, an increase in toughener content results in a decrease in both flexural modulus and flexural strength. In the experiments that involve varying silane coupling agent concentrations, DSC results indicate that as the concentration of the silane coupling agent increases, the curing temperature decreases. The DMA results indicate that as the concentration of silane coupling agent increases, Tg and E’ in the high-temperature range decreases, while E’ in the low-temperature range increases. The TGA results reveal that the thermal stability values at 300°C are not affected by the addition of silane coupling agents. In summary, this study provides valuable information for the development of liquid epoxy molding compounds and lays the foundation for further research.