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研究生： 吳雅婷
Ya-ting Wu
論文名稱： 電漿氧化成長氧化鋁與氧化鋁-氧化銅介電層之單極式電阻切換研究
Investigation of Unipolar Resistive Switching AlOx and AlOx+CuOx Dielectric Layers Growth by Plasma Oxidation
指導教授： 周賢鎧
Shyankay Jou
口試委員: 周振嘉
Chen-Chia Chou
何志浩
Jr Hau He
學位類別： 碩士
Master
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2012
畢業學年度： 100
語文別： 中文
論文頁數： 135
中文關鍵詞： 濺鍍 、電漿氧化 、燈絲導通 、AlOx氧化層 、電阻式記憶體
外文關鍵詞： Sputtering, plasma oxidation, filament conduction, ReRAM
相關次數： 點閱：202  下載：14 
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    • 本研究以Al與Al(Cu 5wt%)靶材濺鍍沉積下電極層，以RF與MW電漿氧化的方式成長電阻層，上電極皆以Al濺鍍，製成Al/AlOx/Al、Al/AlOx+CuOx/Al(Cu 5wt%)三層結構之電阻式記憶體，探討摻Cu對元件的結構與電性之影響。本實驗電極層材料選用Al與摻Cu之Al兩種金屬，與在半導體工業界常用摻1%Cu的Al導線相近，此材料可以直接應用在積體電路製程上。
    當Al/AlOx/Al元件未摻入Cu時，電阻切換操作的 set與reset電壓與電流範圍較不穩定，電阻操作次數約10次左右。當元件下電極摻入Cu時，元件操作之電壓電流穩定，且可循環操作至數百次，高低電阻比值可達10^5倍。高電阻態之電性分析結果認為在低電壓時元件皆為Ohmic導通，高電壓時未摻Cu之元件符合Poole-Frenkel 發射機制；有摻Cu之元件高電壓處以Child’ s law做傳導，與低電壓部分之Ohmic導通合稱空間電荷傳導(Space charge limit current, SCLC)；另一方面，低電阻狀態則皆為Ohmic導通之燈絲型態。在耐性測試方面，有摻Cu之元件耐性較佳，記憶的資訊可儲存長達10年，不會因重複的讀取而損壞。
    由XPS與升溫測試推測，本實驗電漿氧化出之電阻層有未氧化之Al，所以以電阻層中以Al作為主要的導電燈絲成分；當元件電阻層中有Cu存在時，會在接近下電極處開始形成與Al混和的燈絲，因此使得後續電阻切換時切斷與連結燈絲較容易，電性掃描較為穩定。

    To study electrical properties and structural effects on the resistance switch of AlO-based resistance random access memory (ReRAM), we fabricated Al/AlOx/Al and Al/AlOx+CuOx/Al(Cu 5wt%) three-layer structures. The bottom electrode layers were prepared by sputtering Al and Al(Cu 5wt%) target, respectively. The oxide resistor layers were formed by RF and MW plasma oxidation of the bottom electrodes, and top electrode layers were generated by sputtering Al target. In this study, we utilized Al and Cu-doped Al as the electrode layers. They are compatible to Al 1% Cu, which has been utilized for interconnects, in the integrated circuit process.
    The resistance switching operation such as set-reset voltages and current ranges was unstable for the Al/AlOx/Al devices, and it was operated for just about 10 times. When Cu was introduced in the Al/AlOx+CuOx/Al(Cu 5wt%), set-reset voltages and current ranges were stable, and the device could be switched for hundreds of times. The ratio of high resistance state (HRS) and low resistance state (LRS) value for the Al/AlOx+CuOx/Al(Cu 5wt%) is about 105. HRS of these devices were Ohmic conduction at low operation voltages. At high operation voltages, the conduction mechanism was Poole-Frenkel emission for the Al/AlOx/Al, and Child’ law for the Al/AlOx+CuOx/Al(Cu 5wt%) (Ohmic conduction followed by Child’s law is also called Space-charge-limit-current mechanism). LRS of both devices followed Ohmic conduction. In retention test, the device doped with Cu can store information up to 10 years, and it won’t vanish due to repeat readind.
    XPS analysis and temperature tests showed that Al was not oxidized completely during plasma oxidation. Unoxidized Al possibly was the major component in the conduction filament. When the device was doped with Cu, the components of the conduction filament was mixtures of Al and Cu, thus the filament would link and break easier, and the switching process would be more stable.

    摘　要 I Abstract II 目錄 III 圖目錄 VI 表目錄 XI 第一章 前言 1 第二章 文獻回顧 2 2.1 非揮發式記憶體　(Non-Volatile Random Access Memory) 2 2.1.1鐵電式記憶體(Ferroelectric Random Access Memory, FeRAM) 2 2.1.2相變化式記憶體(Phase-Change Random Access Memory, PRAM) 2 2.1.3磁阻式記憶體(Magnetoresistive Random Access Memory, MRAM) 2 2.1.4 電阻式記憶體(Resistive Random Access Memory, ReRAM) 3 2.2 電阻式記憶體的電阻轉換機構與導電機制 5 2.2.1 導電機構介紹 5 2.2.2 導電機制介紹 9 2.3 Al2O3之電阻切換研究 16 2.3.1純Al2O3 16 2.3.2摻雜其他元素的Al2O3 20 2.4 其他介電層摻雜Cu之研究 24 2.5 研究動機 30 第三章 實驗方法與步驟 31 3.1 實驗流程 31 3.1.1 基材清洗 32 3.1.2 磁控式濺鍍鍍膜 32 3.1.3 電漿氧化 34 3.1.4 TEM截面試片製備 36 3.2 實驗儀器簡介 39 3.2.1真空濺鍍製程 39 3.2.2 電漿氧化製程 41 3.3 實驗分析儀器簡介 43 3.3.1 膜厚量測(α-step) 43 3.3.2 X光繞射分析儀 (X-ray Diffractometer) 44 3.2.3 掃描式電子顯微鏡 (Scanning Electron Microscope) 45 3.3.4 X光電子分析儀 (X-ray Photoelectron Spectrum) 46 3.3.5 穿透式電子顯微鏡 (Transmission Electron Microscopy) 47 3.3.6 原子力顯微鏡 (Atomic Force Microscopy) 48 3.4實驗儀器簡表 49 3.5實驗耗材簡表 50 3.6 分析與鑑定 51 3.6.1 薄膜厚度分析 51 3.6.2 薄膜成分分析 51 3.6.3 薄膜表面型態分析 51 3.6.4 截面型態分析 51 3.6.5 電性量測 52 第四章 結果與討論 54 4.1 以MW電漿氧化AlOx與AlOx+CuOx介電層特性分析 54 4.1.1 介電層成分分析 54 4.1.2 介電層結構分析 65 4.1.3介電層表面型態分析 73 4.1.4 摻雜Cu對元件的影響 76 4.2 以MW電漿氧化電阻層之元件電性量測 78 4.2.1 元件掃描路徑分析 78 4.2.2 導電機制分析 82 4.2.3 耐性測試 85 4.2.4 導電燈絲成分分析 89 4.3 以RF電漿處理對元件的影響 94 第五章 結論 99 第六章 未來展望 100 參考文獻 101 附錄 109 Al-Cu Phase Diagram 109 Al-O Phase Diagram 109 JCPDs Card - Al 110 JCPDs Card - Cu 111 JCPDs Card - Al2Cu 112 JCPDs Card - Al2O3 113 JCPDs Card – CuO 114 JCPDs Card – Cu2O 115 Spectrum of XPS – O 116 Spectrum of XPS – Al 117 Spectrum of XPS – Cu 118

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