Pt(100)修飾硫醇分子對銅沉積的影響及 修飾釕對一氧化碳氧化的活性探討;Effect of Pt(100)-modified thiol molecules on copper deposition and the activity of modified ruthenium on carbon monoxide oxidation

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/89169

Title:	Pt(100)修飾硫醇分子對銅沉積的影響及修飾釕對一氧化碳氧化的活性探討;Effect of Pt(100)-modified thiol molecules on copper deposition and the activity of modified ruthenium on carbon monoxide oxidation
Authors:	趙子聿;Chao, Tzu-Yu
Contributors:	化學學系
Keywords:	鉑(100);電鍍銅;硫醇分子;一氧化碳氧化
Date:	2022-08-10
Issue Date:	2022-10-04 11:00:09 (UTC+8)
Publisher:	國立中央大學
Abstract:	半導體製程中最常使用的矽晶圓通常以(100)晶面作為基底來進行後續一步步的製程，隨著線寬逐漸縮小，常常在填孔時產生缺陷，導致產品的良率降低，如果能讓每一步製程都保持整齊的排列堆積，且每一層整齊堆積，搭配有機硫化物對銅沉積的速度及方式進行控制，相信能減少缺陷的產生。本研究使用Pt(100)晶面作為載體，利用循環伏安法(Cyclic Voltammetry，CV)和掃描式電子穿隧顯微鏡(Scanning Tunneling Microscope，STM)，探討Pt(100)上搭配使用無機添加物KCl，以及有機添加物-硫化物(MAA、MPS、MPA)對電鍍銅的影響以及表面的形貌變化。其中在僅有無機添加物時，可以觀察到銅在Pt(100)上有棋盤狀結構的生長方式；在電極上修飾有機硫化物後則沒有棋盤結構的產生，但銅仍然會以(100)的1 × 1結構進行堆積。其中MAA和MPS分子作為加速劑能使銅快速地進行沉積，並且在多層銅上可以觀察到轉置的現象；而MPA分子作為抑制劑完美的抑制了銅的生長，只要電位控制在一定範圍，便可以確保銅的沉積範圍可以被控制。再者，Pt(100)作為催化載體也比Pt(111)晶面效果更好，更多的活性位點，幫助一氧化碳氧化的電位負移，使電池的效率提高，搭配釕金屬的修飾，做出了極佳的催化活性。並觀察一氧化碳在Pt(100)電極上不同電位的吸附模式，3 × 7以及3 × 6結構。並觀察到釕金屬是屬於吸附成核後向上生長的金屬，並不會有層狀堆積。 ;The most commonly used silicon wafer in the semiconductor process is the (100) orientation, on which 3D electronic components are built. As the line width continued to shrink, producing a defect-free Cu fill is challenging. One of aspects of fabricating Cu interconnects involves a thorough understanding of Cu electroplating. Organicthiols have been indispensable ingredient in the formula in Cu deposition bath. However, the effect of these organic additives on the Cu deposition is still lacking. In this study, cyclic voltammetry and scanning electron tunneling microscope (STM) were used to explore the electrodeposition of Cu on a well-ordered Pt(100) electrode in formula containing organosulfur compounds such as mercaptoacetic acid (MAA), mercaptopropane sulfonic acid (MPS), mercaptopropionic acid (MPA). If the formula contained only H2SO4 + CuSO4 + KCl, Cu was deposited in a quasi layered fashion. High resolution STM imaging revealed atomic structures on this smooth Cu deposit, where Cu film arranged in a chessboard structure on Pt(100). All organic additives used in this study resulted in different textures of the Cu deposit and no chessboard structure was observed. Among these additives, MAA and MPS modifiers on the Pt(100) electrode resulted in thicker Cu film than that produced by MPA in the same Cu plating bath. This contrast is reasoned by the reduction rate of Cu2+ at the modified Pt(100) electrode and the segregation rate of additive from the Pt substrate onto the Cu deposit. Moreover, the electrocatalytic activity of Pt(100) toward the oxidation of carbon monoxide was examined. The as-produced Pt(100) electrode is more active than Pt(111) crystal face, as judged from a negative shift of the stripping potential of carbon monoxide. The poisoning effect of CO on Pt catalyst can be alleviated by depositing submonolayer ruthenium species. The spatial structures of CO on Pt(100) were examined by molecular resolution STM imaging.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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