本論文的主要目的為研究並開發出適用於深次微米積體電路製程的下一世代低介電常數材料。吾人利用電漿輔助化學氣相沉積法在矽基材上沉積含氟之有機矽酸鹽玻璃薄膜，同時亦沉積未含氟之有機矽酸鹽玻璃作為對照實驗組。

　　在本論文的第一部分將討論初鍍膜的材料特性。吾人改變不同的沉積溫度及反應前驅物的氟流量，並利用多種分析方式來瞭解初鍍膜的物理及化學特性。在物理特性方面，吾人利用多波長橢圓光學儀來量測鍍膜的厚度及折射率；掃瞄式電子顯微鏡觀察鍍膜截面形態並量測鍍膜厚度；電容–電壓及電流–電壓法來研究鍍膜的介電常數、漏電流強度與崩潰電場強度；奈米壓痕量測器研究鍍膜的機械特性。結果顯示，相較於氟流量的改變，沉積溫度對鍍膜的物理特性有較大的影響，沉積溫度越高，鍍膜的排列越緊密，因此其機械強度與電性表現越佳；而氟流量越高，其結果亦顯示鍍膜的機械強度與電性表現有明顯的改善。在化學特性上，使用X光光電子能譜分析鍍膜的鍵結形態與成份含量；傅利葉轉換紅外線光譜儀分析鍍膜的化學鍵結形態，並從其圖譜中利用主要化學鍵結的相對強度來計算鍍膜中各個成份的相對含量。結果顯示，初鍍膜中的化學鍵結形態與鍵結角度會隨著不同的沉積溫度與氟含量而改變。當沉積溫度越高時，鍍膜的鍵結形態會趨向於較堅固的網狀結構；而氟流量越高時，除了Si–F鍵結的相對強度越強外，Si–O的鍵結位置亦會往高波數的方向移動，即所謂的藍位移。吾人經由上述的實驗結果，推導出可能且合理的反應機構，此反應機構可應用於此一化學反應系統中反應參數的最佳化。

　　在論文的第二部分中，吾人除了探討初鍍膜的熱穩定外，並選擇較佳條件的鍍膜，將其實際地應用在積體電路後段製程整合裡。在鍍膜的熱穩定性方面，吾人將上述不同條件的初鍍膜經過7次的熱處理，藉此模擬介電層在後段製程中所受到的熱應力。再經由上述的物理與化學特性分析，結果顯示較高沉積溫度與氟含量的初鍍膜具有較佳的熱穩定性，而且鍍膜中大多數的不穩定鍵結與未鍵結的游離分子在第一次的熱處理過程裡，便會從鍍膜的結構中移除，使得鍍膜的鍵結形態重整，趨向於更穩定的網狀結構。而在後段製程整合中，吾人使用四點抗彎黏著力測試器量測初鍍膜與其他材料的附著力；除此，並利用黃光與蝕刻的技術，將較佳條件的初鍍膜，定義出雙鑲嵌結構後填入銅導線。其結果顯示本研究中的鍍膜能真正應用於下一世代的積體電路後段製程裡。

　　The objective of this study is to investigate and develop a suitable low dielectric material (Low-k) and its integration for the application of the deep submicron ultra-large scale integrated circuits (ULSI). The fluorine-modified organosilicate glass (FOSG) composite thin films were deposited on silicon substrates by plasma enhanced chemical vapor deposition method (PECVD). The fluorine-free organosilicate glass (OSG) was also deposited for a comparison with the FOSG film.

　　In the first section, the physical and chemical characteristics of the as-deposited films were investigated by varying the deposition temperature and the fluoride flow ratio. In the part of physical characteristics, the thickness and refractive index of the as-deposited films were measured by spectroscopic ellipsometry. The cross-section micrographic and thickness of the composite films were observed by scanning electron microscopy (SEM). The capacitance–voltage (C–V) and current–voltage (I–V) measurements were carried out to investigate the permittivity, leakage current density, and breakdown field strength of the as-deposited films. The nano-indenter was performed to measure the hardness and modulus of the as-deposited films. The results show that the deposition temperature dominates the physical characteristics in comparison with the fluoride flow ratio. As the deposition temperature increases, the solider films can be achieved; and as the fluoride flow ratio increases, the mechanical strength and electrical performance also can be improved. In the chemical characteristics part, the bonding configuration, film composition and quantity of the as-deposited films were determined by X-ray photoelectron spectroscopy (XPS). The Fourier transform infrared spectroscopy (FTIR) was used to study the bonding structure of the composite films. Also, the relative fluorine and carbon content of the films were calculated by the peak height of the main bonding from FTIR spectra, which was agreed with the results of XPS. The results exhibit that the bonding configuration and bonding angle of the composite films varies with different deposition temperature and fluoride flow ratio. As the deposition temperature increases, the porous structure of the films leads to more rigid network structure. As the fluoride flow ratio increases, not only the strength of Si–F peak increases, but also the Si–O peak location shifts to higher wavenumber that is so-called “blue-shift”. According to the aforementioned results, we propose the chemical reactions and mechanisms responsible for the formation of the composite films those can be applied to optimize the process parameters in this system.

　　Not only the thermal stability of the as-deposited film, but also the integration of the backend of line (BEOL) in ULSI process were investigated in the second section. On the thermal stability side, the as-deposited films were subsequently annealed 7 times to simulate the effect of thermal budget on inter-metal dielectric (IMD) in current BEOL scheme. After examining the same physical and chemical characteristics, the results show that the films with higher deposition temperature and fluoride flow ratio lead to superior thermal stability. The unstable and free radicals of the film structure are almost released at the first annealing cycle. The annealing treatments result in the reorganization of film structure and leading the films to more stable network structure. On the side of BEOL integration, four point bending test was used to measure the film adhesion between the composite films and the barrier materials. In addition, the photo-lithography and etching techniques were carried out to pattern the dual Damascene structure and subsequently the interconnection metal was formed by copper filling. The results exhibit that the new Low-k material, FOSG, appears to be a promising low dielectric constant material for IMD application beyond the 130 nm technological node.

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