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研究生: 徐健真
Hsu, Chien-Chen
論文名稱: 有機磁性半導體—富勒烯與鈷的交互作用探討
Organic magneto-semiconductor: Interaction between Fullerene and Cobalt.
指導教授: 林文欽
Lin, Wen-Chin
口試委員: 莊子弘
Chuang, Tzu-Hung
藍彥文
Lan, Yann-Wen
林文欽
Lin, wen-chin
口試日期: 2022/07/14
學位類別: 碩士
Master
系所名稱: 物理學系
Department of Physics
論文出版年: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 119
中文關鍵詞: 有機-磁性介面磁性半導體原子力顯微儀柯爾磁光效應拉曼光譜儀光致螢光光譜Co-C60 複合材料磁阻量測霍爾效應
英文關鍵詞: Organic-magnetic interface, Magnetic-semiconductor, MOKE, AFM, Co-C60 composite, Magnetoresistance, Raman spectrum, Photoluminescence, Hall effect
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202201493
論文種類: 學術論文
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在自旋電子學中,磁性半導體是其中一個重要研究領域,其中有機材料與磁性材料的電子交互作用,是如何影響有機-磁性複合材料的磁性與電子傳輸行為,更是一個需要深入探討的領域。本研究使用物理氣相沉積法 ( Physical Vapor Deposition, PVD ),於超高真空系統 ( Ultra-High vacuum system, UHV ) 中,選擇在Al2O3 與Si兩種基板上,成長了C60/Co/C60與C60/Co的三層膜與雙層膜結構。透過探討薄膜磁性、表面形貌、光致螢光光譜( Photoluminescence, PL ) 與拉曼光譜 ( Raman Spectrum ) 、電壓-電流性質、磁阻響應與霍爾效應 ( Hall effect ) 在不同溫度的真空熱退火前後的變化,並以共鍍方式成長了不同比例的Co-C60 複合材料,並與上述退火實驗結果進行比較。
本實驗分為兩大主軸,第一部分為C60薄膜與C60/Co 層膜在500 ℃ 下的真空退火,由表面形貌量測中,發現成長於Al2O3基板的C60/Co 雙層膜於退火後,形成了以Co原子為主的奈米島分區結構,以及C60 薄膜經過退火後,形成了近十奈米的原子團簇;在使用拉曼光譜分析碳基材料振動模式後,發現C60裂解為無定型碳的程度,因Co原子的參與下變得更高,說明了Co與C原子之間的交互作用,不僅增強了C60的裂解行為,同時限制了無定型碳的脫附行為;在磁滯曲線量測中,經過500 ℃ 退火後薄膜鐵磁行為明顯增強,包含了矯頑場 ( Coercivity, Hc ) 增大了至少5倍以上,以及薄膜由無磁性/順磁性轉變為鐵磁性;在光致螢光光譜量測中,可觀察到C60 與無定型碳之PL峰值強度皆受到Co原子的含量影響;在電壓-電流特性的量測中,注意到C60/Co 雙層膜無論退火前後皆屬於導體;在磁阻量測中,注意到退火後C60/Co 雙層膜磁阻率增大了將近50 %;在霍爾效應量測中,C60/Co 雙層膜經過500 ℃ 退火後,薄膜主要載子由電洞變為電子,並量測到載子濃度為2.32 × 1021 cm-3,載子遷移率為10.9 cm2V-1s-1。
第二部分則是製作不同比例的Co-C60 複合材料,並注意到Co原子比例越低,薄膜內材料就以蕭特基接觸為主,以及C60分子的發光特性受到Co原子的熱蒸鍍過程破壞,最後則是C60在共鍍過程中受到Co-C60電子交互作用影響,導致C原子間的鍵能改變,進而改變C60的分子振動模式。
上述實驗結果說明了Co與C60的交互作用增強了C60的裂解行為,且C60裂解後所形成的無定型碳,與Co原子混合後誘發了更明顯的磁性行為,同時在光學量測發現退火後的C60/Co仍保有半導體性質,暗示了只要適當調整Co原子與C60含量,就可利用真空退火製作出以Co-C為主成分的磁性半導體,對改善有機自旋閥中的電導率不匹配,具有相當大的潛力。

In spintronics, magneto-semiconductor is an important part of the connection with spin and devices. To improve the conductivity mismatch between metal and organic semiconductor (OSC), the electrion interaction organic-magnetic interface is a potential solution. In this thesis, we choose Al2O3 and Si substrate to prepare C60/Co/C60 tri-layer and C60/Co bi-layer structure with physical vapor deposition in an ultra-high vacuum system. Through the analysis of morphology image, magnetism, Photoluminescence (PL), Raman spectrum, I-V curve, MR and Hall effect, we compare these results before and after annealing in vacuum.
There are two main parts in the experiment setup. One is the annealing experiment of C60 thin film, C60/Co/C60 tri-layer and C60/Co bi-layer. During 1 hour annealing at 250 ℃, 500 ℃ and 750 ℃, morphology image show the nanostructural transition of C60/Co/Al2O3 and the columnar-like structure of C60 thin film after annealing at 500 ℃;MOKE reveal that the enhancement of magnetism in C60/Co and C60/Co/C60, such as the amplification of coercivity;PL exhibited cobalt atom reduced the PL intensity of C60;In the Raman spectrum analysis, we observe the characteristic peak shift of C60 which illustrate the formation of amorphous carbon;I-V curve show that C60/Co is a conductor weather it is annealed or not;MR show the MR ratio of C60/Co bi-layer enhanced about 50 % after annealing at 500 ℃;Hall effect measurement show that after annealing at 500 ℃, the majority carrier of C60/Co changed from hole to electron.
The other part is the preparation of Co-C60 composites. First we notice that the lower content of cobalt would cause more schottky contact in the composites. Then we observet the chacteristics peak of C60 was reduced by the cobalt atom deposition by the PL measurement. Finally, the raman vibration mode of C60 is shift at least 20 cm-1 by the electrion interaction of cobalt and C60.
The morphology show the interaction between cobalt and C60 enhance the formation of amorphous carbon. Annealing in vacuum contribute to the stronger magnetism due to the mixture of cobalt and amorphous carbon. In additional, PL and Raman show that semiconductor properties remain after annealing. By controlling the ratio of cobalt and C60, we can make Co-C magnetic-semiconductor by annealing in vacuum.

第1章 緒論 1 1-1 C60簡介 1 1-1-1 發現 1 1-1-2 基本性質 3 1-1-3 應用領域 8 1-2 自旋電子學簡介 ( Spintronics introduction ) 9 1-2-1 自旋電子學與有機半導體[26] 9 1-2-2 有機自旋閥 ( Organic Spin valves ) 13 1-2-3 自旋介面交互作用 ( Spinterface )[13][26] 16 1-3 研究動機 18 1-3-1 C60與過渡金屬原子的介面交互作用 18 1-3-2 C60的熱處理 19 第2章 實驗技術與基礎原理 21 2-1 超高真空系統 ( Ultra-High Vacuum System ) 21 2-2 電子束熱蒸鍍法 ( E-beam Evaporation ) 23 2-3 磁滯曲線 ( Hysteresis loop ) 25 2-4 磁性物質 ( Magnetic materials ) 26 2-4-1 強磁 26 2-4-1-1 鐵磁性 ( Ferromagnetism ) 27 2-4-1-2 亞鐵磁性 ( Ferrimagnetism ) 28 2-4-2 弱磁 29 2-4-2-1 順磁性 ( Paramagnetism ) 29 2-4-2-2 抗磁性 ( Diamagnetism ) 29 2-4-2-3 反鐵磁性 ( Antiferromagnetism ) 30 2-5 磁異向性 ( Magnetic anisotropy ) 31 2-5-1 磁晶異向性 ( Magnetocrystalline anisotropy ) 32 2-5-2 形狀異向性 ( Shape anisotropy ) 32 2-5-3 誘導異向性 ( Induced anisotropy ) 32 2-5-4 應力異向性 ( Stress anisotropy ) 32 2-6 導電性質 ( Electrical properties ) 33 2-6-1 磁阻簡介 ( Magnetoresistance effect ) 33 2-6-1-1 常磁阻 ( Ordinary Magnetoresistance, OMR ) 34 2-6-1-2 異向性磁阻 ( Anisotropic Magnetoresistance, AMR ) 34 2-6-1-3 巨磁阻 ( Giant Magnetoresistance, GMR ) 35 2-6-1-4 超巨磁阻 ( Colossal Magnetoresistance, CMR ) 36 2-6-1-5 穿隧式磁阻 ( Tunneling Magnetoresistance, TMR ) 37 2-6-2 霍爾效應 ( Hall effect ) 39 第3章 儀器介紹 42 3-1 柯爾磁光效應顯微儀 ( Magnetic Optical Kerr Microscope ) 42 3-1-1 磁光效應緣起 42 3-1-2 柯爾磁光效應 ( Magneto Optical Kerr Effect, MOKE ) 原理 42 3-2 原子力顯微鏡 ( Atomic Force Microscopy, AFM ) 47 3-2-1 原子力顯微鏡緣起 47 3-2-2 原子力顯微鏡原理 47 3-2-3 原子力顯微鏡操作 48 3-2-3-1 接觸模式( Contact Mode ) 49 3-2-3-2 非接觸模式( Non-contact Mode ) 49 3-2-3-3 輕敲模式( Tapping Mode ) 49 3-3 光致螢光光譜儀 ( Photoluminescence, PL ) 50 3-3-1 光致螢光原理 50 3-4 拉曼光譜儀 ( Raman Spectrum ) 52 3-4-1 拉曼光譜原理 52 3-5 電性量測 ( Electrical properties measurement ) 53 第4章 實驗設計 54 4-1 基板清潔 ( Preclean ) 54 4-1-1 基板擦拭 54 4-1-2 超音波震洗 54 4-2 薄膜成長 55 4-2-1 超高真空環境 55 4-2-2 鍍膜速率校正 55 4-2-3 圖案化沉積 56 4-3 量測與退火流程 58 4-3-1 樣品結構與量測項目 58 4-3-2 真空退火流程 59 第5章 實驗結果與討論 60 5-1 10 nm C60分別在Co薄膜、矽基板及藍寶石基板上成長後,經500 ℃,1小時高真空退火後的形貌分析 60 5-1-1 討論:高真空退火對薄膜形貌造成的影響 63 5-1-2 討論:Co-C新型複合材料的形成可能性 64 5-2 10 nm C60分別在Co薄膜、矽基板及藍寶石基板成長後,經500℃,1小時高真空退火後的拉曼光譜比較 65 5-2-1 討論:C60分子振動模式經退火後發生的變化 67 5-2-2 討論:C60裂解行為的增強與Co原子之間的關係 67 5-3 10 nm C60分別在Co薄膜、矽基板上成長後, 經500℃,1小時高真空退火後的光致螢光光譜比較 68 5-3-1 討論:高真空退火對薄膜半導體性質造成的影響 70 5-4 C60 / Co層膜經500 ℃,1小時高真空退火前後的磁滯曲線比較 73 5-4-1 討論:高真空退火後,薄膜磁性行為的變化 78 5-5 C60 / Co層膜經500℃,1小時高真空退火後的電學性質 82 5-5-1 電壓-電流特性 82 5-5-2 磁阻響應 84 5-5-3 霍爾效應 85 5-5-4 討論:C60 / Co 雙層膜於退火前後的電學性質 88 5-6 Co-C60複合材料與C60 / Co層膜的表面形貌、磁性、光學性質比較 91 5-6-1 以不同比例成長之Co-C60複合材料表面形貌 91 5-6-1-1 Co-C60複合材料與C60 / Co層膜的表面形貌整理 93 5-6-2 以不同比例成長Co-C60複合材料之磁性行為 94 5-6-3 以不同比例成長之Co-C60複合材料光學性質 95 5-6-3-1 拉曼光譜比較 95 5-6-3-2 光致螢光光譜比較 96 5-6-4 討論:由Co-C60複合材料成長所觀察到的現象整理 97 5-7 Co-C60複合材料的電學性質 100 5-7-1 Co-C60複合材料電壓-電流曲線 100 5-7-2 Co-C60複合材料的磁阻響應 101 5-7-3 討論:Co比例對Co-C60複合材料電學性質的影響 101 第6章 結論與未來展望 103 6-1 結論 103 6-2 未來展望 104 第7章 參考資料 105 第8章 補充資料 112 8-1 C60 拉曼振動模式種類 112 8-2 以C60 為間隔層的有機自旋閥應用[83,84,85] 113 8-3 C60 在不同基板上脫附所需的溫度 115 8-4 Co-C60 複合材料之相關研究 116

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