臺灣博碩士論文加值系統

當今的積體電路內連接導線之製作流程為離子化濺鍍TaN/Ta阻障層及銅晶種層、電鍍（或無電鍍）銅導線。但在面對未來技術節點持續精進，以及溝槽尺寸持續下降（僅約35~65 nm）的情況下，這種乾濕結合的銅鑲嵌流程已面臨諸多困境（如阻障層過厚及銅導線填充性不足）；採用無電鍍（Electroless Plating）所生長的鈷合金阻障層因催化微粒的尺寸極限（3 nm），而使最小厚度止於5 nm，距離未來所需之‘近零厚度’門檻仍有一段距離，本論文提出以APTMS-SAM充當晶種吸附層及銅擴散阻障層，此種製程不但有積層結構較簡單的優點，且厚度僅1.6 nm。
本論文首先以平面試片進行SC-1化學溶液處理試片，使試片表充滿羥基，以利APTMS分子生長，後續對試片表面之APTMS-SAM進行SC-1溶液處理，對其表面進行改質，使其能順利固定Ni催化晶種，並催化生長無電鍍銅薄膜。後續將此「APTMS-SAM/Cu」試片進行不同溫度的退火處理，量測其整體片電阻變化，並以純銅試片為對照組，所得之結果證實，APTMS-SAM能有效阻擋銅的擴散行為，其臨界溫度由400℃提升至500℃。
後續將此製程導入溝槽導線製作，其尺寸為：深500 nm、線寬100 nm、線長25 m。將完成溝槽填充之試片進CMP處理，去除試片表面之銅膜，得到完整填充之銅導線，再以重量百分濃度為10 % 的雙氧水對銅膜進行表面處理，以及在銅膜表面生長APTMS-SAM，最終取得吾人所需之完整包覆APTMS-SAM的銅線試片。
最後將純銅導線、局部包覆APTMS-SAM及完整包覆APTMS-SAM的銅線試片分別進行CCS實驗，此三種試片的崩潰時間分別為580秒、1650秒及2850秒，此結果證實APTMS-SAM確實能增加銅導線的可靠度。

Currently, sputter deposited TaN/Ta and electrochemically plated Cu metallization layers are the key interconnection thin-film materials for integrated circuits. However, in the face of future technology nodes scaling continues to decline, this wet and dry combination of copper inlay process has faced many difficulties (such as the barrier layer is too thick). The electroless plating cobalt alloy barrier layer is limit by the catalytic particles (3 nm) size.
In this paper, SC-1 chemical solution was used to prepare the sample, and the sample was filled with hydroxyl group to facilitate the growth of APTMS. The APTMS solution on the surface of the sample was treated with SC-1 solution. Modified, so that it can be successfully to catch Ni catalytic seeds, and deposed electroless copper film.
This process was subsequently introduced into the trench wafer (500 nm deep, line width is 100 nm and a line length is 25 μm). After completed to fill the grooved sample we uesd CMP to remove the surface copper of the sample, get a complete filled copper wire, and then used the weight percentage of 10% hydrogen peroxide to treat the copper film surface, and growth of APTMS-SAM on the copper film surface, and ultimately to obtain the complete coating of APTMS-SAM copper wire sample.
Finally, CCS experiments were carried out on pure copper wire, APTMS-SAM partially-capping copper wire and APTMS-SAM all-capping copper wire, respectively. The collapse time of the three sample was 580 s, 1650 s and 2850 s. The results confirmed that APTMS -SAM does increase the reliability of copper wires.

誌謝 I
摘要 II
Abstract IV
第一章 緒論 2
第二章 文獻回顧 5
2.1 大馬士製程 5
2.2 奈米晶種技術 6
2.3 自組裝單層應用 8
2.3.1自組裝單層原理 8
2.3.2自組裝單層之阻障強化 9
2.3.3自組裝單層之晶種固定技術 12
2.4 銅導線填充 14
2.5 可靠度分析介紹 15
2.5.1可靠度簡介 15
2.5.2可靠度評估方法 16
第三章 實驗步驟與分析原理 26
3.1 試片整體製作流程 26
3.2個別步驟說明 26
3.2.1 p-SiOCH介電層基材準備 26
3.2.2 溝槽試片製作 27
3.2.3化學溶液表面改質 28
3.2.4 p-SiOCH之矽烷化 28
3.2.5自組裝單層表面羥基化 29
3.2.6催化晶種生長 29
3.2.7無電鍍銅填充 30
3.2.8化學機械研磨（CMP）處理 30
3.2.9銅導線全面APTMS-SAM披覆 31
3.3試片分析及儀器介紹 31
第四章 低k介電層平面試片分析 39
4.1 SC-1溶液羥基化處理對p-SiOCH之親水性與電性影響 39
4.1.1表面親水性變化分析—水接觸角量測 39
4.1.2絕緣性分析—J-E量測 40
4.1.3介電常數（k）變化分析 41
4.2 p-SiOCH之矽烷化（silylation）過程分析 43
4.2.1表面形貌與親水性變化分析 43
4.2.2 表面鍵結分析 45
4.3 自組裝單層之羥基化程度對晶種吸附之影響 53
4.3.1 SC-1處理時間對APTMS-SAM之鍵結改變效應 54
4.3.2 SC-1處理（羥基化）程度對晶種吸附能力之影響 56
4.4 晶種吸附機制及其相變化分析 57
4.5 無電鍍銅析鍍及其表面之APTMS-SAM生長行為 61
4.6 介電層溝槽填充 64
4.7 可靠度分析 66
4.7.1整體片電阻量測 66
4.7.2 定電流應力量測（CCS） 67
第五章 結論 108
參考文獻 110

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