本研究利用二階段法合成6FDA基含氟聚亞醯胺共聚物。利用控制BisAAF及PPD二胺之成份比例，與6FDA合成具不同結構之含氟聚亞醯胺。首先，對於含氟聚亞醯胺，分析其化學結構、成份、介電常數、玻璃轉換溫度、在空氣及N2下之5%熱裂解溫度、吸水性、機械性質、常見溶劑中之溶解度及在可見光範圍之光穿透率等基本特性。之後，利用濺鍍沉積5nm厚之Cr及Ta於6FDA-BisAAF及6FDA-PPD含氟聚亞醯胺上，透過X光光電子能譜儀觀察金屬與含氟聚亞醯胺之界面化學鍵結行為。在本研究的第三個部分利用O2及N2電漿處理對含氟聚亞醯胺做表面改質，探討經不同電漿處理後之含氟聚亞醯胺其表面化學結構的變化及表面水氣吸附行為。此外，經電漿處理前後之含氟聚亞醯胺將製作成金屬-絕緣體-半導體(MIS)結構，量測其漏電流行為。最後，本研究中探討低溫退火(低於含氟聚亞醯胺玻璃轉換溫度)及不同退火氣氛對含氟聚亞醯胺之影響。利用電容-電壓(C-V)量測對缺陷的敏感特性，觀察低溫退火參數對含氟聚亞醯胺之影響。
由傅立葉轉換紅外線光譜儀的結果發現，本研究中之聚醯胺酸前驅物在經300℃ 1h之環化反應後，將完全轉變為聚亞醯胺。透過控制不同的單體比例將可以改變6FDA-BisAAF-PPD含氟聚亞醯胺共聚物之材料特性。隨著PPD含量的增加，6FDA-BisAAF-PPD含氟聚亞醯胺共聚物之玻璃轉換溫度由6FDA-BisAAF之317℃，提升到6FDA-PPD之365℃。含氟聚亞醯胺之機械強度亦隨著PPD含量的增加而上升。本研究中所合成之含氟聚亞醯胺在N2下的5%重量損失則介於530-540℃。6FDA-BisAAF-PPD含氟聚亞醯胺共聚物之介電常數值亦隨著PPD的含量的增加而升高，從6FDA-BisAAF之2.63上升至6FDA-PPD之2.87(@1MHz)。而本研究中所有之含氟聚亞醯胺在可見光波長範圍大於500nm時，皆可達到90%的光穿透率。
經由X光光電子能譜儀的分析可以發現，在Cr及Ta金屬濺鍍過程中，電漿所造成之離子轟擊將會破壞C-CF3鍵結，造成含氟聚亞醯胺表面的去氟化反應。經離子轟擊所形成之斷鍵將會與沉積之金屬形成metal-C鍵結。此外，Cr及Ta沉積至含氟聚亞醯胺表面時亦會與聚亞醯胺結構中之羰基(C=O)反應而形成C-O-metal鍵結。透過熱力學的考量，將可以預測金屬與含氟聚亞醯胺間之界面反應及其可能產生之鍵結型態。
分析經不同電漿處理之含氟聚亞醯胺可以發現，具不同結構之含氟聚亞醯胺在受到相同電漿處理時之反應極為類似。由實驗結果可以發現，O2電漿將會與含氟聚亞醯胺中的C原子反應形成C-O鍵結，並進一步破壞含氟聚亞醯胺表面結構。另一方面，N2電漿與含氟聚醯亞之反應性則多屬物理性之離子轟擊。N2電漿所造成表面不穩定鍵結將增加含氟聚亞醯胺之水氣吸附，進一步影響含氟聚亞醯胺之介電常數及漏電行為。
為了了解退火參數對含氟聚亞醯胺之影響，6FDA-PPD/Si在經不同氣氛之熱處理(N2+H2及真空退火)後，利用硬式光罩沉積Cu電極製作Cu/6FDA-PPD/Si MIS電容器並量測其C-V曲線。由C-V曲線的結果可以發現，隨著退火溫度的增加，將會造成6FDA-PPD內正電荷的增加，導致平帶電壓往負電壓方向偏移。再次量測經存放在空氣一周時效處理後試片之C-V曲線則可以發現，所有試片之C-V曲線將會往理想C-V曲線方向偏移。相較於真空退火處理，N2+H2氣氛退火具有消除在熱處理中所產生之缺陷能力，並且在經空氣時效處理後有較低之介電常數表現。當應用6FDA-PPD含氟聚亞醯胺作為電子元件中之介電材料，熱處理的溫度及條件皆必須加以仔細評估及考慮。

In this study, 6FDA-based fluorinated copolyimides were synthesized with different ratios of BisAAF, PPD diamines by a two-step method. Properties such as chemical structure, composition, dielectric constant, glass transition temperature, thermal decomposition temperature, water absorption, tensile properties and transmittance were investigated by using Fourier transform infrared spectrometry (FTIR), elemental analysis, impedance spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), tensile tester and UV-visible spectrophotometry. In the second part of the experimant, interfacial reaction between metals and fluorinated polyimides were examined by X-ray photoelectron spectroscopy (XPS) after thin metal films (5nm-thick Cr and Ta) were deposited onto the fluorinated polyimides. In addition, effects of O2 and N2 plasma surface modification on fluorinated polyimides were also investigated. XPS and thermal desorption spectroscopy (TDS) were used to examine the surface chemical states and water adsorption of these polyimides after O2 and N2 plasma treatment. The polyimides with or without plasma treatment, were made into metal-insulator-semiconductor (MIS) to investigate their leakage current behavior. Finally, capacitance-voltage (C-V) characteristics of Cu/6FDA-PPD/Si structure after different temperature annealing process were examined.
The FTIR results suggest that all poly(amic acid) precursors are converted into polyimide after curing at 300℃ for 1h. Fluorinated polyimdes with different properties can be obtained by controlling the molar ratios of the monomers. The glass transition temperature(Tg), modulus, and tensile strength increase with increasing PPD content. The values of Tg increase from 317oC of pure 6FDA-BisAAF polyimide to 365oC of pure 6FDA-PPD polyimide. The 5% weight loss of fluorinated polyimides ranges from 530-540℃ in N2 atmosphere. Dielectric constants increase from 2.63 of pure 6FDA-BisAAF to 2.87 of pure 6FDA-PPD. The transmittances of all fluorinated polyimides are greater than 90% at the wavelength above 500nm.
Metal(Cr, Ta)-fluorinated polyimide interfacial reactions were investigated by XPS. XPS reveals that metal-C, C-O and metal-O bondings are presented in metallized fluorinated polyimides. Disappearance of the C-F bonding is attributed to the disruption of CF3 side groups from these polyimides when they are exposed to the plasma during the metal deposition. Nevertheless, the disruption of CF3 side groups also creates sites for the formation of metal-C bondings. Cr and Ta may react with the C=O bondings in the imide structure and forming C-O-metal bondings after reaching the polyimide surface. The reactions between metal and polyimides can be predicted through thermodynamical calculation.
Surface modification of 6FDA-based fluorinated polyimides by O2 or N2 plasma was carried out and the material characteristics of the surfaces after plasma treatment were investigated. X-ray photoelectron spectroscopy analysis reveals that O2 plasma will react with carbon atoms in the polyimide structure to form C-O bonding on the surface and destroy the polyimide structure. On the other hand, chemical reactions between nitrogen and fluorinated polyimides are not obvious. The unstable bonds created by the N2 plasma treatment may absorb more H2O molecules and degrade electrical characteristics.
Finally, the capacitance-voltage (C-V) characteristics of Cu/6FDA-PPD/Si metal-insulator-semiconductor (MIS) capacitors after different annealing processes were investigated. During annealing (in N2 + H2 ambient and in vacuum), positive charges are generated in the capacitors and it leads to a shift of flat-band voltage (VFB) toward the negative bias direction. However, the VFB of the annealed samples moves backward (the positive bias direction) after aging at room temperature in air for 1 week. Comparing with vacuum annealing, N2+H2 annealing can reconstruct the broking bonds created during annealing and reveal a lower dielectric constant after aging in air for 1 week. Therefore, when applying 6FDA-PPD as dielectrics in microelectronic devices, one must be careful on the annealing condition and the service temperature even though it is well below the Tg.

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