萬本儒Wang, Ben-Zu臺灣大學:化學工程學研究所龔建豪Kung, Chien-HaoChien-HaoKung2010-06-302018-06-282010-06-302018-06-282009U0001-2007200917075800http://ntur.lib.ntu.edu.tw//handle/246246/186983　低介電常數材料在現今半導體工業中扮演相當重要的角色，其中在鹼性環境下以多階段水熱法製備之孔洞結晶型二氧化矽薄膜具有介電常數低、機械強度佳以及製程整合簡單的優點，相當具有發展潛力。但由於目前相關的程序仍相當冗長，因此本研究將改以單階段水熱法，研究水熱反應時間、離心程序等因素對於孔洞結晶型二氧化矽薄膜的影響。　由研究結果發現，單階段的水熱反應所產生的奈米粒子其均勻性較差且粒徑較大，因此本研究導入離心程序來篩選適合鍍膜的奈米粒子。但結果顯示，離心程序在篩選奈米粒子的同時，也會改變粒子的濃度、結晶性及溶液的黏度，進而對薄膜性質造成影響。本研究的其他發現簡述如下，第一是水熱反應時間越久，薄膜總孔洞體積越大且顆粒彼此間堆疊的大孔隙越多，除了會造成較大的漏電流外，也可能因金屬的滲透而影響介電常數之量測；第二是結晶性越高，顆粒表面的氫氧基越少，因此薄膜機械強度越差；第三是較厚的薄膜可能會有表面修飾不完全的問題，因此介電常數無法降低；第四是離心後取上層液塗佈所得到的薄膜其介電常數較低、機械強度越高且漏電流較小，而中層比上層之各項性質差，但仍比未離心者佳。　在製程中同時使用界面活性劑與離心程序除了可以藉由增加總洞體積而達到降低介電常數值的效果外，也可以有效地避免大孔隙的產生並增加塗佈之均勻性。　本研究中的最佳結果在水熱反應時間36~42小時，離心後取上層液塗佈，所得之薄膜具介電常數1.78~1.88，Hardness 1.33~1.46 Gpa，Elastic module 11.10~12.72 Gpa，漏電流密度1.37e-8~4.97e-8 A/cm2。該薄膜的各項性質皆符合未來IC工業所需之標準。Low dielectric constant (low-k) material is important in semiconductor industry. Crystalline porous silica which is prepared by two stages hydrothermal process in base environment possesses advantages of low dielectric constant, good mechanical strength, and easily-preparation procedures. However traditional synthesis process is very tedious, and some procedures are not necessary actually. In the present study, an one stage hydrothermal method is used, and the effects of hydrothermal process and centrifugation on the properties of crystalline porous low-k silica thin film were examined.t was found that the size, concentration, and crystallinity of the particles are proportional to hydrothermal period. Also the particle size is less uniform than what is prepared by two stage process. After the reaction, the solution containing particles was centrifuged, and it showed that centrifugation process would influence the crystalline, concentration of particle and viscosity of solution. However, the followings were observed: First, longer hydrothermal time would result in higher porosity in thin film and more large voids from particles piled up each other which would result in serious leakage current and influence the measurement of k value. Second, the better crystalline of particles in the colloid would cause the mechanical strength poor, since pooler hydroxide groups on particle surface. Third, thicker thickness of film might result in the process of surface modification incomplete, and the dielectric constant couldn’t be decreased. Finally, the film derived from the solution taken from the upper side of centrifugation tube after centrifuged was used for the spin-coating on silicon wafer. The film possesses lower k value and leakage current density and higher mechanical strength than the film spun by the solution un-centrifuged.he processes applying surfactant and centrifugation both could not only decrease k value by increasing the total pore volume in the film, but also decrease quantity of large voids, and facilitate the coating situation on the surface.he best thin films prepared in this research possess the k value of 1.78~1.88, hardness of 1.33~1.46Pa, elastic modulus of 11.10~12.72Gpa, and leakage current of 1.37e-8~4.97e-8 A/cm2. The films were derived by taking the upper side solution of centrifugation tube after centrifuged, and the solution were synthesized under the hydrothermal conditions, temperature 100℃ for 36~42 hours.摘要 Ibstract II錄 IV目錄 VII目錄 XI一章 緒論 1-1研究背景 1-2 研究目標 4二章 文獻回顧與研究設計 5-1 低介電薄膜材料 5-2 孔洞型二氧化矽材料 9-3 Surfactant-templating method合成中孔洞二氧化矽低介電薄膜 10-4 Hydrothermal method合成具沸石結構之二氧化矽低介電薄膜 13-5 結合surfactant-templating與hydrothermal method 15-6 研究設計 18三章 實驗方法 19-1 實驗藥品及儀器 19-1.1 藥品 19-1.2 實驗儀器 20-2 實驗程序與合成條件 21-2.1 矽晶片的清洗程序 21-2.2 合成旋塗溶液 22-2.3 旋轉塗佈(Spin coating) 22-2.3 熱處理:軟烤與鍛燒(Baking and Calcination) 22-2.4 表面修飾 23-3 薄膜鑑定 25-3.1顯微鏡觀察 25-3.2 電性量測 25-3.3 機械強度量測系統 28-4 X光粉末繞射實驗 30-5氮氣吸脫附實驗 32-6 膠體粒子粒徑與濃度分析實驗 33四章 結果與討論 34-1抽氣過濾及界面活性劑的加入時機對薄膜性質的影響 34-2水熱反應時間與離心程序對粒子粒徑與濃度大小的影響 37-2.1 水熱反應時間與離心程序對奈米粒子粒徑的影響 39-2.2水熱反應時間與離心程序對奈米粒子濃度的影響 42-3水熱反應時間與離心程序對薄膜性質的影響 46-3.1水熱反應時間與離心程序對薄膜介電常數的影響 47-3.2 水熱反應時間與離心程序對薄膜機械強度的影響 51-3.3 水熱反應時間與離心程序對薄膜漏電流的影響 56-4 奈米粒子結晶性、薄膜孔洞體積及孔徑分佈之數據分析 61-4.1 奈米粒子結晶性之數據分析 62-4.2 薄膜孔洞體積之數據分析 69-4.3 薄膜孔徑分佈之數據分析 74五章 結論 86六章 未來展望 88-1 熱處理程序的改進 88-2 表面修飾程序的改進 89-3 減少薄膜內部孔洞崩塌 90七章 參考文獻 913001998 bytesapplication/pdfen-US低介電常數界面活性劑沸石孔洞材料離心程序鹼式法low dielectric constantthin filmsurfactantzeoliteporous materialcrystallinecentrifugationbase environmentone stage hydrothermal methodthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/186983/1/ntu-98-R96524004-1.pdf