臺灣博碩士論文加值系統

銅製程之出現乃因半導體晶片上原有之鋁導線材料面臨瓶頸，當製程技術縮小至0.25微米甚至更小，導線寬度也隨之變窄，鋁之高阻值（r=2.8mW-cm）特性使得訊號傳輸時間愈來愈長，在IC產品對速度要求極高之特性下，導電性極佳之銅（r=1.7mW-cm）將成為下一代導線技術之主要材料。銅金屬薄膜製程包含物理氣相沈積法（physical vapor deposition；PVD）、化學氣相沈積法（chemical vapor deposition；CVD）與電鍍法等。然目前銅金屬沈積之技術趨勢乃為利用具有低成本和低阻值優勢之銅電鍍法（electroplating）完成。於銅電鍍沈積之前，需先沈積一層連續且階梯覆蓋性良好之銅晶種層（seed layer），以利後續之電鍍銅可於其上成長。
本研究之目的乃在探討以無電極電鍍法成長銅晶種層於擴散阻障層--氮化鈦（titanium nitride；TiN）之特性研究。本研究並發展以矽非晶相（amorphous silicon；a-Si）為置換層，進行銅接觸置換（contact displacement）反應，改善直接於TiN表面成長銅活化層易形成島狀結構之缺點。本研究更以無致毒性之乙醛酸（glyoxylic acid）與二甲基胺硼烷（dimethylamine borane；DMAB）取代習用具高揮發性之致癌物--甲醛（formaldehyde）做為還原劑，於含有銅離子源、錯合劑、安定劑與界面活性劑等物質之電鍍液在攝氏60度的溫度下，進行無電極銅電鍍，而可於被活化之表面成長銅晶種層。此銅晶種層之存在，除提供導電層外，並能提供銅之成核層，以利後續以電鍍法將銅成長於其上。
本論文所涵蓋之分析技術有：（1）以X光繞射儀（X-ray Diffractometer；XRD）測定晶體化學結構、（2）以掃瞄式電子顯微鏡（Scanning Electron Microscope；SEM）研究表面形態、（3）以歐傑電子能譜儀（Auger Electron Spectrometer；AES）做縱深成分分布分析、（4）以X光光電子能譜儀（X-ray Photoelectron Spectrometer；XPS）分析化學能態與（5）以原子力顯微鏡（Atomic Force Microscope；AFM）探討表面形態。藉由上述之量測分析技術，得以探討利用無電極電鍍法成長銅晶種層之特性。

The emergence of copper manufacturing process has come about because of the existent bottleneck of the aluminum material used for the conducting wires on semiconductor chips. As the manufacturing processes reduce the component size in ICs to less than 0.25 mm, the width of conducting wires reduces accordingly. The high resistivity of aluminum prolongs the time needed for signal transmission. To meet the strict demand for IC products, copper with superior electric conductivity will surely be a very important material used for conducting techniques. Different manufacturing processes of copper membranes include physical vapor deposition (PVD), chemical vapor deposition (CVD), electroplating and so on. For the time being, however, the trend of copper deposition is in electroplating, which is cost efficient and of low resistivity. Before electroplating, however, it is necessary to deposit a seed layer which is consecutive and of good step coverage in order to grow electroplated copper afterwards.
The purpose of this research is to explore the properties of copper seed layer grown by electroless plating on titanium nitride (TiN). Also, this research intends to develop a displacement layer made of amorphous silicon (a-Si), and process copper contact displacement to improve the island structure of copper activated layer which can then be grown directly on the surface of TiN. Furthermore, this research proposes glyoxylic acid and dimethylamine borane (DMAB) as replacements to formaldehyde, which is commonly used at present as a reductant but regarded as a carcinogen and is of high volatility. The copper seed layer will be grown by the electroless plating method on the activated surface of TiN, at the set temperature of 60°C with the plating bath consisting of the copper source, complexing agent, stabilizer, surfactant and so on. The existence of copper seed layer provides not only the conduction layer, but also the copper nucleation layer, to help the growth of electroplated copper on the surface of TiN.
The analysis techniques utilized in this thesis include: (1) X-ray Diffraction (XRD) for determining the crystal structure; (2) Scanning Electron Microscopy (SEM) for studing the surface morphologies; (3) Auger Electron Spectroscopy (AES) for investigating the depth profile; (4) X-ray Photoelectron Spectroscopy (XPS) for analyzing the chemical energy state and (5) Atomic Force Microscopy (AFM) for exploring the surface morphologies. With the above technique analyses, the properties of copper seed layer utilizing the electroless plating method can be understood satisfactorily.

第一章 緒論 1
1-1 IC發展概況及趨勢 1
1-2 銅製程旭日東升 4
1-3 電子遷移效應對銅導線可靠度之影響 6
1-4 國內外之發展現況 7
1-5 銅導線製作技術 10
1-6 無電極電鍍銅之簡介 12
1-6.1 無電極電鍍之原理 12
1-6.2 催化層（敏化與活化）之製備 12
1-6.3 鍍浴之組成與特性 15
1-6.4 無電極電鍍銅之反應機制 18
1-7 專利地圖之製作 19
1-8 本研究目的 20
第二章 實驗方法及儀器分析原理 31
2-1 化學藥品 31
2-2 基材（substrate） 31
2-3 基材之前處理 31
2-3.1 清洗（cleaning） 31
2-3.2 活化（activation） 34
2-4 無電極電鍍銅之鍍浴組成 34
2-5 分析儀器及其量測原理 34
2-5.1 X光繞射儀 34
2-5.2 掃瞄式電子顯微鏡 38
2-5.3 歐傑電子能譜儀 39
2-5.4 X光光電子能譜儀 40
2-5.5 原子力顯微鏡 42
第三章 結果與討論 44
3-1 於TiN表面成長銅晶種之研究 44
3-3.1 基材鑑定 44
3-1.2 利用接觸置換法活化基材表面及其特性研究 47
3-1.3 於活化表面進行無電極銅電鍍及其特性研究 47
3-2 附著性之改善 52
3-2.1 10%HF水溶液之蝕刻處理 52
3-2.2 於蝕刻處理過之基材表面進行活化反應及其特性研究 52
3-2.3 無電極銅電鍍之晶種層與其特性研究 58
3-3 矽非晶相層之引入 58
3-3.1 基材鑑定 58
3-3.2 於矽非晶相表面進行銅接觸置換反應及其特性研究 61
3-3.3 無電極銅電鍍成長晶種層及其特性研究 66
第四章 結論 80
參考文獻 81

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