臺灣博碩士論文加值系統

　　目前地球環境持續惡化且日益受到注視的情況之下，減少能源消耗以及綠色環保將是未來科技發展不容忽視的重要課題。
　　本論文乃利用具生物親合性的聚賴胺酸(Poly-L-Lysine, PLL)與聚穀胺酸(Poly-L-Glutamic acid, PLGA)作為媒介材料，以逐層組裝技術(Layer by Layer, LbL)鍍製聚胺基酸多層薄膜於二氧化矽基板上，並利用此薄膜輔助合成金奈米粒子以及矽氧化物，最後使用溶膠凝膠法製備二氧化鉿控制氧化層並鍍製上鋁電極後，即完成奈米晶體記憶體元件。此製程的特點為水相全溶液製程，過程中不需使用到有機溶劑且製程相當簡便，相當符合近年來綠色化學的趨勢。我們主要探討了以下實驗參數：(1)聚胺基酸的還原能力，(2)聚胺基酸薄膜的鍍製特性，(3)還原金奈米粒子之影響條件，(4)金奈米粒子穩定性探討，與(5)奈米晶體記憶體特性探討。
　　由實驗結果得知：(1)聚穀胺酸的還原能力較聚賴胺酸優，且分子量愈低所還原的金奈米粒子粒徑較小。若比較官能基的還原能力方面，帶有負電荷的(COO-)羧基應較氨基(NH3+)為強；(2) 高分子量聚胺基酸所鍍製的薄膜愈均整，且聚賴胺酸為頂層薄膜時，薄膜的粗糙度較低；且在不同的酸鹼值環境下鍍製的結果也有所不同；(3) 在酸鹼值約為6時以聚胺基酸薄膜所得到的奈米粒子條件最佳，平均粒徑為4.5nm，整體密度為1.72ⅹ1012cm-2；(4)利用聚胺基酸薄膜析出的矽氧化物能使金奈米粒子具備一定的熱穩定性；(5)在記憶元件特性探討中，奈米粒子密度較高展現出的特性愈佳。

Under the continued deterioration of the global environment and the increasingly getting more attention, reducing energy consumption and environmental protection will be an important issue in the future technological development.
In this work, we used biocompatible Poly-L-Lysine (PLL) or Poly-L-Glutamic acid (PLGA) as medium. The multilayers of PLL/PLGA were fabricated by applying Layer-by-Layer (LbL) assembly process on SiO2 substrate. The formation of gold nanoparticles and silica were both mediated by the polypeptide multilayers. After covering the nanoparticles by spin coating of sol-gel-synthesized HfO2 control oxide, Al electrode was deposited to construct a nanocrystal memory device. This study proposed a water-based all-solution process without the use of organic solvent. This process is quite simple and consistent with the recent trend of green chemistry. In this study, several issues are discussed as below: (1) the reducing ability of poly amino acid, (2) characterization of the multilayer film of poly amino acid, (3) reduction conditions of gold nanoparticles, (4) stability of gold nanoparticles, (5) memory properties of nanocrystal memory.
The experimental results showed : (1) Reducing ability of PLGA is stronger than that of PLL. And the reducing ability of carboxyl group is stronger than that of amino group by comparing the characterization of functional group in poly amino acid. The poly amino acid with a lower molecular weight induced the formation of gold particle with smaller particle size. (2) The poly amino acid with higher molecular weight assembled to a smoother film, but also depending on the solution pH value. (3) A superior reduction result of gold nanoparticles with average particle size about 4.5nm and total particle density of 1.72ⅹ1012cm-2 was obtained at solution pH value about 6. (4) The poly amino acid mediated silica can serve as protection layer, improving the thermal stability of gold nanoparticles. (5) The nanocrystal memorywith higher particle density showed better memory property.

目錄 I
表目錄 VI
圖目錄 VII
中文摘要 1
英文摘要 3
第一章 研究緒論 5
1.1前言 5
1.2研究動機 7
1.3論文架構 9
第二章 文獻回顧 13
2.1記憶體沿革 13
2.1.1揮發性記憶體 (Volatile memory, VRAM)[15-16] 14
2.1.2非揮發性記憶體 (Non-volatile memory, NVRAM)[17-18] 14
2.1.3記憶體性能之指標 15
2.2奈米晶體記憶體 16
2.3奈米粒子簡介 18
2.3.1奈米粒子的發展與歷史 19
2.3.2金奈米粒子的製備法 19
2.3.3奈米粒子的製備 20
2.3.3.1物理方法 20
2.3.3.2化學方法 21
2.3.3.3綠色化學法 22
2.4胺基酸簡介 23
2.4.1胺基酸的選擇 25
2.4.2聚賴胺酸(Poly-L-Lysine)簡介 25
2.4.3聚榖胺酸(Poly-L-Glutamic acid)簡介 26
2.5逐層組裝(Layer-by-Layer)原理 26
2.5.1逐層組裝技術的應用 27
2.5.2鍍製方法 29
2.5.2.1浸鍍法(Dip coating) 29
2.5.2.2旋鍍法(Spin coating) 29
2.6高分子輔助合成奈米粒子發展 30
第三章 實驗方法 44
3.1實驗藥品與材料 44
3.2實驗用晶片處理流程 45
3.2.1矽晶片表面清洗[68] 45
3.2.1.2二氧化矽氧化層的成長 47
3.2.2二氧化矽氧化層的清洗 47
3.2.3二氧化矽氧化層的處理 48
3.3聚胺基酸還原力之探討 48
3.4鍍製聚胺基酸薄膜 48
3.4.1聚胺基酸溶液的調配 48
3.4.2聚胺基酸單層薄膜的鍍製(monolayer) 49
3.4.3聚胺基酸多層薄膜的鍍製(multilayer) 49
3.5奈米粒子之製備 49
3.5.1氯金酸溶液配製與浸鍍 49
3.5.2保護氧化層的覆蓋 49
3.6去除聚胺基酸薄膜 50
3.6.1熱處理 50
3.6.2氧電漿處理 50
3.7奈米晶體記憶體元件之製備 50
3.7.1控制氧化層之鍍製 51
3.7.2電極的鍍製 51
3.8分析儀器 51
3.8.1紫外光-可見光吸收光譜儀(UV-vis Spectrometer) 51
3.8.2橢圓偏光儀(Ellipsometer) 52
3.8.3掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 53
3.8.4 X光繞射儀(X-ray diffraction, XRD) 53
3.8.5原子力顯微鏡(Atomic force microscope, AFM) 54
3.8.6電容-電壓量測(C-V量測) 54
3.8.7圓二色光譜儀(Circular Dichroism Spectropolarimeter, CD) 55
3.9試片代號 55
第四章 結果與討論 61
4.1水溶液中聚胺基酸還原力探討 61
4.1.1聚賴胺酸與聚穀胺酸還原能力測試 61
4.1.2聚賴胺酸於微酸性環境下還原能力 62
4.2聚胺基酸薄膜鍍製探討 63
4.2.1聚胺基酸薄膜於不同酸鹼環境下鍍製狀況 64
4.2.2聚胺基酸薄膜的組裝特性 65
4.3奈米粒子之製備 66
4.3.1聚胺基酸薄膜還原特性探討 66
4.3.1.1薄膜形貌對還原特性影響 67
4.4氯金酸溶液pH值對還原特性之影響 68
4.4.1氯金酸水溶液pH值之影響 68
4.5氯金酸濃度對還原特性之影響 69
4.6金奈米粒子之穩定性探討 70
4.7氧化層穩定奈米粒子特性探討 70
4.8奈米晶體記憶體特性探討 71
4.8.1記憶特性分析 71
4.8.2浸鍍氯金酸時間對記憶元件特性探討 72
4.8.2.1閘極電壓對ΔVFB之影響 73
第五章 結論 96
第六章 參考文獻 98

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