因應積體電路技術持續發展，面臨效能改進與製程挑戰，技術的成本和複雜性持續增加，並且積體電路不斷縮小，訊號傳輸的速度已經達到極限，為降低積體電路中金屬連線電阻及連線間絕緣層之電容所造成的速度延遲，半導體業早已開始使用銅內連線及低電容值之低介電絕緣材料，然而隨著運算需求不斷提升，銅金屬內連線也難以負荷，學界與業界開始探討新的材料以用於銅導線之擴散阻礙層，例如二維材料、高熵合金，以及新的內連線材料，例如鎳、鈷、釕、鉬及介金屬和MAX相，目前已經有許多研究耐火合金作為擴散阻礙層或是耐火元素作為內連線的研究，然而對於耐火合金的電性的研究有限，且耐火介金屬也未曾被討論，因此本研究探討一元至多元的耐火元素、合金電性差異，並設計釕基的耐火介金屬，討論多元效應對於電子平均自由路徑的影響，以及了解材料本質電阻率的影響因子，並嘗試形成新的介金屬以了解其相結構穩定性，藉由數種材料釐清高熵合金及釕基的耐火介金屬是否有機會做為金屬內連線材料，透過磁控濺鍍沉積一元至五元耐火元素、合金薄膜，透過電性量測，分析不同材料間的差異及合金內部的原子差異對電性所造成的影響，再透過磁控共濺鍍沉積釕與一元耐火元素及釕與二元合金所形成的介金屬薄膜，在800℃、1000 ℃ 一分鐘快速熱退火後形成介金屬相，並對相結構進行分析，再使用Fuchs-Sondheimer和Mayadas-Shatzkes模型進行擬合 (Fitting) 分析，發現多元合金以及釕與二元合金所形成的介金屬之電子的平均自由程非常短，較短的電子平均自由路徑使電子散射程度大幅降低，有效抑制了尺寸效應。

In response to the continuous development of integrated circuit (IC) technology, there are ongoing challenges in performance improvement and manufacturing processes. The cost and complexity of technology are increasing, and with the continuous miniaturization of ICs, the speed of signal transmission has reached its limit. To reduce speed delays caused by the resistance of metal interconnections and the capacitance of the insulating layer between connections, the semiconductor industry has long been using copper interconnections and low-dielectric constant materials. However, as computing demands continue to rise, copper metal interconnections are also becoming difficult to handle. Academia and industry are beginning to explore new materials for diffusion barrier layers of copper wires, such as two-dimensional materials, high-entropy alloys, and new interconnection materials like Co and Ru, intermetallic compounds, and MAX phases. Numerous studies have investigated refractory high-entropy alloys as diffusion barrier layers or refractory elements as interconnections. However, research on the electrical properties of refractory alloys is limited, and Ru-based refractory intermetallic compounds have not been discussed. Therefore, this study explores the electrical differences between unitary to multicomponent refractory materials and alloys and aims to design and develop Ru-based refractory intermetallic compounds. It discusses the impact of high-entropy effects on the electron mean free path and identifies the factors affecting the intrinsic resistivity of materials. Additionally, it attempts to form new intermetallic compounds to understand their phase structure stability, clarifying whether multicomponent alloy and Ru-based refractory intermetallic compounds have the potential to be used as metal interconnection materials.
This research used magnetron sputtering deposition of mono-element to five-element refractory materials and alloy thin films, electrical measurements were conducted to analyze the differences between various materials and the impact of atomic differences within the alloys on their electrical properties. Subsequently, Ru-1B and Ru-2B intermetallic thin films were deposited through magnetron co-sputtering. After rapid thermal annealing at 800°C and 1000°C for 1 minute to form intermetallic phases, the phase structure was analyzed. Using the Fuchs-Sondheimer and Mayadas-Shatzkes models for fitting, it was found that the average free path of electrons is very short. Compared to pure metals, the shorter average free path of electrons significantly reduces electron scattering, effectively suppressing the size effect.

摘要 I
Abstract III
目錄 V
圖目錄 IX
表目錄 XVII
壹、前言 1
貳、文獻回顧 3
2-1 積體電路內連線發展近況 3
2-1-1 金屬內連線材料 3
2-1-2 電阻電容延遲效應-RC Delay 5
2-1-3 金屬內連線-介電材料 7
2-1-4 銅內連線-雙鑲嵌製程 9
2-1-5 銅內連線-電化學鍍覆 (ECP) 11
2-1-6 銅內連線-擴散阻障層 13
2-2 影響內連線電阻率因素 15
2-2-1 體電阻率 Bulk resistivity (ρ0) 15
2-2-2 合金電阻率-雜質散射 17
2-2-3 介金屬電阻率-有序結構影響 20
2-2-4 Matthiessen’s rule 21
2-2-5 表面散射-Fuchs Sondheimer Model 23
2-2-6 晶界散射-Mayadas Shatzkes Model 26
2-2-7 電子平均自由路徑 (EMFP，λ) 31
2-2-8 電阻溫度係數 (TCR) 33
2-3 新金屬內連線材料 36
2-3-1 銅內連線製程技術之困境 36
2-3-2 純金屬作為內連線之研究 40
2-3-3 合金作為內連線之研究 47
2-3-4 介金屬作為內連線之研究 49
2-4 高熵合金電性與發展潛力 54
2-4-1 高熵合金介紹 54
2-4-2 高熵合金薄膜 57
2-4-3 高熵介金屬 62
2-5 研究目的 64
參、實驗步驟 65
3-1 實驗規劃 65
3-1-1 成分選擇 66
3-2 實驗流程 70
3-2-1 靶材製備 70
3-2-2 基板準備 71
3-2-3 試片基本性質 72
3-2-4 金屬薄膜沉積 73
3-2-5 真空熱處理 75
3-2-6 GIXRD晶體結構定 76
3-2-7 EPMA組成成分分析 77
3-2-8 SEM薄膜表面形貌觀察 78
3-2-9 AFM薄膜厚度觀察 79
3-2-10 聚焦離子束 (FIB) -TEM試片製備 80
3-2-11 TEM薄膜微結構觀察與成分分析 81
3-2-12 四點探針電阻率量測 82
3-2-13 電阻溫度係數量測 83
肆、結果與討論 84
4-1 1B-5B 耐火金屬、合金性質分析 84
4-1-1 元素、合金鍍率分析 84
4-1-2 XRD晶體結構定 87
4-1-3 EPMA組成成分分析 90
4-1-4 SEM表面形貌觀察 92
4-1-5 厚膜電阻率討論 95
4-1-6 薄膜電阻率討論 100
4-1-7 電阻溫度係數 (TCR值) 分析 105
4-2 Ru-1B與Ru-2B 性質分析 107
4-2-1 Ru 金屬鍍率分析 107
4-2-2 XRD晶體結構鑑定 109
4-2-3 TEM-EDS組成成分分析 113
4-2-4 TEM微結構觀察 115
4-2-5 厚膜電阻率討論 121
4-2-6 薄膜電阻率討論 123
4-2-7 TCR值分析 128
伍、結論 131
陸、參考文獻 133

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