臺灣博碩士論文加值系統

半導體製程隨著摩爾定律不停進步，提升電晶體密度的同時，也微縮了金屬導線的尺寸，在小線寬的情況下電阻率(ρ_0)會急遽上升，高電阻金屬與介電層產生寄生電容，造成電阻電容延遲。同時小線寬會使電子在金屬導線中產生較大的散射，是由於電子在金屬中移動，碰到晶界或表面而導致的散射後產生二次電子，其行走的距離為電子的平均自由路徑。在現今常使用之銅金屬在中段製程中已無法滿足現今需求，由於銅在窄線寬下會提高本身的電阻率，以及其電子平均自由路徑(λ)較長，而鈷和釕較銅相比具有較高的抗電致遷移能力以及低平均自由路徑，因此被作為替代先進製程的材料。
本研究以共濺鍍法製備鈷、鈷(釕)合金，控制釕的成份獲得不同成分的鈷(釕)合金，通過3d軌域的金屬釕來強化鈷連導線，摻入的釕含量從1.28 at.% 至45.23 at.%，並使用二氧化矽基板及氮化鈦鎢做黏附層與阻障層，同時比較常溫以及基板加熱400 oC，用以獲得最佳鈷、鈷(釕)合金薄膜。將鈷及鈷(釕)合金薄膜利用感應耦合電漿質譜儀進行成份分析，四點探針系統量測薄膜片電阻，X光繞射進行相結構分析，掃描式電子顯微鏡觀測薄膜形貌， X 光光電子能譜作為原子鍵結之判定，並量測 IV、和崩潰電壓薄膜電性。
由以上實驗結果得知，在所有鈷釕合金薄膜中，經基板加熱400 oC 並經 700 oC退火5分鐘後，成分由低到高之電阻率分別為，純鈷 : 8.0 μΩ-cm ； Ru – 1.28 at.% : 26.2 μΩ-cm ； Ru – 1.68 at.% : 28.8 μΩ-cm ； Ru – 2.34 at.% : 42.9 μΩ-cm ； Ru – 16.85 at.% : 49.7 μΩ-cm ； Ru – 36.27 at.% : 59.3 μΩ-cm； Ru – 45.23 at.% : 41.6 μΩ-cm； Ru : 10.4 μΩ-cm ，最低之電阻率為 Ru – 1.28 at.% : 26.2 μΩ-cm。 在中含量釕摻雜鈷釕合金薄膜，相較於無基板加熱，有基板加熱可維持薄膜形狀完整無破裂，且隨著釕含量的上升皆維持六方最密堆積結構，並皆為 HCP (100)、及 HCP (101)繞射面。在微量釕摻雜鈷釕合金薄膜中，Ru – 1.28 at.% 具有高熱穩定性，薄膜完整無破裂。

The semiconductor manufacturing process continues to advance with Moores Law, increasing transistor density while also shrinking the size of metal wires. Under conditions of narrow line widths, resistivity (ρ0) rises sharply, and high-resistance metals cause higher parasitic capacitance with dielectric layers, leading to resistive-capacitive delays. Additionally, nano wires cause greater electron scattering in metal wires, as electrons moving through the metal encounter grain boundaries or surfaces, resulting in secondary electrons. The distance traveled by these secondary electrons is determined by the average free path of the electrons. Currently, copper, commonly used in the middle-of-line, can no longer meet todays demands, as its resistivity increases under narrow line widths and its average free path (λ) is relatively long. In contrast, cobalt and ruthenium exhibit higher resistance to electromigration and shorter average free paths compared to copper, making them suitable materials for advanced process replacements.
This study employed a co-sputtering method to prepare cobalt and cobalt-ruthenium alloys, controlling the ruthenium composition to obtain different compositions of cobalt-ruthenium alloys. The ruthenium content ranged from 1.28 at.% to 45.23 at.%. Using Si/SiO2 substrates with TiWN were used as adhesion and barrier layers, respectively. The study compared room temperature and substrate heating at 400oC to obtain the optimal cobalt and cobalt-ruthenium alloy films. The composition analysis of the cobalt and cobalt-ruthenium alloy films was conducted using inductively coupled plasma mass spectrometry. The film resistance was measured using a four-point probe, X-ray diffraction was employed for structural analysis, scanning electron microscopy was utilized for observing film morphology, X-ray photoelectron spectroscopy was employed for atomic bonding determination, and film electrical properties such as IV, and breakdown voltage were measured.
Above experimental results, it is known that among all cobalt-ruthenium alloy films, after heating the substrate to 400 °C and annealing at 700 °C for 5 minutes, the resistivity from low to high is as follows pure cobalt : 8.0 μΩ-cm ; Ru – 1.28 at.% : 26.2 μΩ-cm ; Ru – 1.68 at.% : 28.8 μΩ-cm ; Ru – 2.34 at.% : 42.9 μΩ-cm ; Ru – 16.85 at.% : 49.7 μΩ-cm ; Ru – 36.27 at.% : 59.3 μΩ-cm ; Ru – 45.23 at.% : 41.6 μΩ-cm ; Ru : 10.4 μΩ-cm. The lowest resistivity is Ru – 1.28 at.% : 26.2 μΩ-cm. In cobalt-ruthenium alloy films with medium ruthenium doping, compared to those without substrate heating, heating the substrate maintains the integrity of the film without cracking, and as the ruthenium content increases, the hexagonal close-packed structure is maintained, with HCP (100) and HCP (101) diffraction planes present. In the micro ruthenium-doped cobalt-ruthenium alloy films, Ru – 1.28 at.% exhibits high thermal stability, with the film remaining intact and crack-free.

摘要......i
Abstract......ii
誌謝......iv
目錄......v
表目錄......vii
圖目錄......viii
第 一 章 緒論......1
1.1 前言......1
1.2 研究動機......3
第 二 章 理論基礎和文獻回顧......4
2.1 半導體先進製程......4
2.2 金屬連導線趨勢......6
2.2.1 鈷與鈷合金......6
2.2.2 釕與釕合金......7
2.2.3 金屬間化合物 (ntermetallic compound)......7
2.3 物理氣相沉積(Physical vapor deposition, PVD)......9
2.3.1 蒸鍍 (Evaporation)......9
2.3.2 離子鍍 (Ion Plating)......9
2.3.3 濺鍍系統 (Sputtering System)......10
2.4 濺鍍產率及氬離子轟擊率 (Sputtering Yield and Ar+ bombardment rate)......12
2.5 薄膜生長......15
2.6 電化學腐蝕......16
2.6.1 極化曲線 (Polarization Curve)......16
2.6.2 電化學交流阻抗 (Electrochemical Impedance Spectroscopy,EIS)......16
第 三 章 實驗流程及儀器介紹......18
3.1 實驗材料......18
3.1.1 實驗基板......18
3.1.2 實驗藥品......18
3.1.3 濺鍍靶材......18
3.1.4 製程氣體......18
3.2 實驗流程......19
3.2.1 實驗前處理......19
3.2.2 製備二氧化矽 (SiO2)......19
3.2.3 濺鍍氮化鈦鎢黏附層......19
3.2.4 濺鍍鈷釕合金薄膜......19
3.2.5 快速退火熱處理RTA......20
3.2.6 電化學腐蝕測試......20
3.3 分析儀器......24
3.3.1 四點探針 (Four-Point Probe , FPP)......24
3.3.2 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)......27
3.3.3 X光繞射分析儀 (X-ray Diffraction , XRD)......28
3.3.4 感應耦合電漿質譜儀 (Inductively coupled plasma-mass spectrometer, ICP-MS)......30
3.3.5 X 射線光電子能譜儀 (X ray Photoelectron Spectroscopy, XPS)......31
3.3.6 表面輪廓儀 (α-step)......32
3.3.7 接觸角和表面張力儀 (Contact Angle and Surface Tension Instruments)......33
3.3.8 多功能聚焦離子束系統 (Focused Ion Beam system, FIB)......34
3.3.9 高解析掃描穿透式電子顯微鏡 (Field Emission Scanning Transmission Electron Microscope, TEM/STEM)......35
第 四 章 實驗結果與結論......36
4.1 氮化鈦鎢阻障層分析......36
4.2 鈷釕合金薄膜成分分析......39
4.3 中含量釕鈷釕合金......41
4.3.1. 中含量釕摻雜鈷釕合金薄膜電阻率......41
4.3.2. 中含量釕摻雜鈷釕合金薄膜表面形貌......43
4.3.3. 中含量釕摻雜鈷釕合金薄膜相分析......55
4.3.4. 中含量釕摻雜鈷釕合金薄膜 XPS 分析......60
4.3.5. 中含量釕摻雜鈷釕合金薄膜表面能......66
4.4 微量摻雜鈷釕合金......67
4.4.1. 微量摻雜鈷釕合金薄膜電阻率......67
4.4.2. 微量摻雜鈷釕合金薄膜表面形貌......69
4.4.3. 微量摻雜鈷釕合金薄膜相分析......79
4.4.4. 微量摻雜鈷釕合金薄膜 XPS 分析......86
4.4.5. 微量摻雜鈷釕合金薄膜 TEM 分析......92
4.4.6. 微量摻雜鈷釕合金薄膜表面能......102
4.4.7. 微量摻雜鈷釕合金薄膜電化學腐蝕......103
4.4.8. 微量摻雜鈷釕合金薄膜 IV 特性......109
第 五 章 結論......110
參考文獻......111
Extended Abstract......119

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