利用同步形成法製備聚亞醯胺/二氧化鈦奈米混成薄膜之特性分析與界面黏著性質之探討

Abstract

中文摘要 隨著科技日新月異的進步，舊有材料的性質已不敷使用，許多研究因而著手於新世代材料的開發，其中，利用溶膠-凝膠法所製備之奈米混成材料可應用在許多新的領域中，也受到最多的注意。本論文研究主要分為三個部分：(1)利用溶膠-凝膠法製備同步形成之聚亞醯胺/二氧化鈦奈米混成薄膜及特性分析。(2)聚亞醯胺/二氧化鈦奈米混成薄膜之物理性質與動態機械特性之研究。(3)聚亞醯胺/二氧化鈦奈米混成薄膜與金屬銅之界面黏著特性之探討。 本研究係利用溶膠-凝膠技術之自催化水解/縮合反應，來製備同步形成之聚亞醯胺/二氧化鈦奈米混成薄膜。並加入乙醯基丙酮當作螯合劑，其目的是藉由鈦烷氧化物與乙醯基丙酮形成一錯化合物，來降低鈦烷氧化物的水解速率，以期望達到均勻分善的效果。第一個部分所使用的二胺及二酸酐分別是：2,5-bis(4-amino-phenyl)1,3,4-oxadiazole (BAO)以及4,4´-oxydiphthalicanhydride (ODPA)。將兩者合成所得的聚亞醯胺酸摻入鈦烷氧化物與乙醯基丙酮混合物，最後利用熱聚亞醯胺化法製得聚亞醯胺/二氧化鈦奈米混成薄膜。並且針對混成薄膜的組織型態、二氧化鈦粒子大小和分佈，以及二氧化鈦的含量多寡對混成膜之光學特性和熱性質的影響加以探討。 本文第二部分主要是由二胺4,4'-diaminodiphenylether (ODA)，與選用三種不同結構的二酸酐，並且導入不同含量的二氧化鈦(介於1至9重量百分比)，合成出三個不同系列的聚亞醯胺/二氧化鈦奈米混成薄膜。這部分著重於不同的聚亞醯胺結構以及二氧化鈦含量多寡，對聚亞醯胺/二氧化鈦奈米混成薄膜特性的影響，例如：熱膨脹係數、熱穩定性、機械強度、動態機械性質以及介電特性等等。 論文最後一個部分是針對聚亞醯胺/二氧化鈦奈米混成薄膜與金屬銅的界面黏著特性作一系列完整的討論。另外，為了進一步提升混成薄膜與銅之間的黏著強度，本研究加以採用電漿表面處理法，希望藉由不同的電漿處理來改質聚亞醯胺/二氧化鈦奈米混成薄膜的表面特性。並且針對不同的二氧化鈦含量與電漿處理法所造成的表面粗糙度、表面能以及黏著強度的變化，逐一加以探討。此外，對於混成薄膜與金屬銅之間的破裂模式、破裂面的界面組成成分，以及破裂面的表面型態做一說明。

Abstract A new polyimide/titania (PI/TiO2) nano hybrid film has been successfully fabricated through the in situ formation of TiO2 within a polyimide matrix by sol-gel process. By using catalyst-free polymerization, acetylacetone (acac) is employed to reduce the hydrolysis rate of titanium alkoxide through the formation of an acetylacetate complex.

The nano hybrid films of TiO2 in polyimide from 2,5-bis(4-amino-phenyl)1,3,4- oxadiazole (BAO) and 4,4´-oxydiphthalic anhydride (ODPA) are synthesized and characterized with regard to the chemical states, average sizes, and spatial distribution of TiO2 particles. The TiO2 content in the hybrid films can be as high as 40 wt%. Moreover, the thermal and optical properties of the hybrid films are compared with those of host polyimide.

Another three series of PI/TiO2 hybrid films are synthesized to facilitate the study of several structure/property responses, including the thermal expansion, mechanical properties, viscoelastic transitions, and electrical properties. These hybrid films are based on 4,4'-diaminodiphenylether (ODA) and various dianhydrides and incorporated with TiO2 content from 1 wt% to 9 wt%. The effect of TiO2 content on the aforementioned properties is also investigated.

The work presented herein also attempts to investigate the adhesion strength between the PI/TiO2 hybrid films and copper system. The influence of TiO2 content on the surface roughness, surface energy as well as adhesion strength is studied. To improve the adhesion strength, modification of plasma treatment (Ar, Ar/N2, and Ar/O2) is also applied to the hybrid films. The changes in surface morphology, surface energy, chemical composition, and peeled-off failure mode as a result of plasma etching are observed. Finally, based on the results of this research, recommendations are made for the future work.