臺灣博碩士論文加值系統

隨著半導體科技的發展，銅製程技術要達成至更小深寬比之填充能力，因此電化學原子層沉積被開發出來沉積原子層級的薄膜，在銅製程未來發展上具有相當的潛力。
本實驗利用電化學原子層沉積 Cu(Mn) 薄膜在直流濺鍍的圖案化Ru基板上。製程中首先利用欠電位沉積 (UPD) 製作一層 Cu 原子層，再 UPD 一層Pb原子的犧牲層，以開路電位通入銅溶液60 s 利用表面侷限氧化還原反應 (SLRR) 將Pb原子置換成 Cu 原子，再以Mn UPD 鍍上疊層，重複 50 循環形成 Cu(Mn) 薄膜，最後以不同 Cu(Mn) 疊層及不同Mn UPD 電位做探討。實驗分析由 X 光電子能譜儀 (XPS) 進行成份分析、I-V 曲線量測電性、X 光繞射分析儀 (XRD) 結構分析、掃描式電子顯微鏡 (SEM)觀察表面形貌。
實驗結果顯示以電化學原子層沉積可成功製備出圖案化 Cu(Mn) 薄膜，以5Cu1Mn 不同Mn UPD 線寬 200 μm的 Cu(Mn) 薄膜，可在 500℃退火下得到最低電阻率。電阻率分別為純 Cu (13.10 μΩ-cm)、Mn-600 (26.60 μΩ-cm)、Mn-700 (45.20 μΩ-cm)、Mn-800 (56.45 μΩ-cm) 和Mn-900 (60.35 μΩ-cm)。

Copper metallization needs comformal deposition in a high aspect-ratio gap / holewhen the device continents to scale down. Electrochemical atomic layer deposition has been used to deposit film layer by layer to meet the requirement for Cu internection.
In this study, theCu (Mn) thin films were deposited on patterned Ru substrates by electrochemical atomic layer deposition. The first Cu layer was deposited by an underpotential deposition initially, followed by a underpotential deposition of Pb to be a sacrificial layer. After that an open circuit potential for 60 s was used to enable a redox replacement of UPD-Pb layer by Cu2+ in a copper solution, and followed by an underpotential deposition ofMn. Cu(Mn) film was formed by repeating the sguences for the 50 cycles. The film composition was determined by an X-ray photoelectron spectroscopy (XPS), the resistance was measured bya current-voltage curve (I-V curve), and crystal structure was analyzed by X-ray diffraction (XRD). The surface morphology was observed by scanning electron microscope (SEM).
Cu(Mn) film can be prepared in pattern substrate by EC-ALD. In this study for 5Cu1Mn, Cu(Mn) thin films on 200 μm line had the lowest resistivity after annealing at 500℃. The lowest resistivity of 13.10 μΩ-cm, 26.60 μΩ-cm, 45.20 μΩ-cm, 56.45 μΩ-cm and 60.35 μΩ-cm for pure Cu, Mn-600, Mn-700, Mn-800, and Mn-900, respectively.

摘要........................i
Abstract....................ii
誌謝..........................iv
目錄.......................................v
表目錄...............................ix
圖目錄.......................x
第一章緒論 ....................1
1.1 前言 ....................1
1.2 研究動機 ....................2
第二章文獻探討.................... 6
2.1 電化學沉積法的原理.................... 6
2.1.1 氧化還原反應 ....................6
2.1.2 電鍍溶液（Plating Bath）.................... 7
2.2 循環伏安法 (Cyclic Voltammetry, CV) 介紹 ....................7
2.2.1 循環伏安法 ....................7
2.2.2循環伏安介紹 ....................8
2.3 欠電位沉積 (Underpotential Deposition, UPD)........................................ 9
2.4 表面侷限氧化還原反應(Surface Limited RedoxReplacement, SLRR) ........................................10
2.5 電化學沉積 (Electrochemical Deposition, ECD) ...11
2.6 原子層沉積 (Atomic Layer Deposition, ALD) ........................................12
2.7 電化學原子層沉積 (Electrochemical Atomic Layer Deposition, ECALD) ....................13
2.8 EC-ALD研究現況 ....................15
2.9 Cu(Mn) 薄膜之文獻探討 ....................15
第三章實驗流程與設備介紹 ....................19
3.1 實驗流程 ....................19
3.2 電化學原子層沉積 (EC-ALD) Cu(Mn) 薄膜製程設定 20
3.2 實驗材料 ....................23
3.2.1 濺鍍靶材 ....................23
3.2.2 基板 ....................23
3.2.3 製程氣體 ....................23
3.2.4化學藥品 ....................23
3.3 實驗設備 ....................24
3.3.1 磁控濺鍍系統 ....................24
3.3.2 電化學原子層沉積 (EC-ALD) 系統 ........................................25
3.3.3 熱處理系統 ....................25
3.4 實驗分析設備 ....................26
3.4.1 三端元件 (MOSFET) 電壓電流 I-V 量測系統 (MOSFET IV) ........................................26
3.4.2 X光繞射分析儀 (X-Ray Diffraction, XRD)... 27
3.4.3 X-ray光電子能譜儀 (X-ray Photoelectron Spectroscopy, XPS) ........................................27
3.4.4 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) .......................................................28
第四章實驗結果與討論 ....................33
4.1以EC-ALD 製備銅(錳)薄膜在線寬200 μm之探討........................................ 33
4.1.1 實驗流程 ....................33
4.1.2 離子鍍液 CV 圖之探討 ....................34
4.1.3 電流-電壓-時間 (I-V-T) 圖分析 ........................................36
4.1.4 電性分析 ....................37
4.1.5 相結構分析.................... 39
4.1.6 表面形貌分析 ....................41
4.1.7 Cu(Mn) 薄膜 XPS 鍵結分析 ....................43
4.2以EC-ALD 製備銅(錳)薄膜在線寬10μm之探討.................... ............................................................45
4.2.1 實驗流程 ....................45
4.2.2 離子鍍液 CV 圖之探討.................... 46
4.2.3 電流-電壓-時間 (I-V-T) 圖分析 ....................48
4.2.4 電性分析 ....................49
4.2.5相結構分析 ....................50
4.2.6 表面形貌分析 ....................51
4.3 綜合分析 ....................53
4.3.1 剝離曲線....................53
4.3.2 成核機制 ....................54
第五章 結論......................110
參考文獻.........................112
Extended Abstract..............123
簡歷 (CV) .....................127

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