臺灣博碩士論文加值系統

奈米氧化鋅粒子因其具有與塊材迥異的光電性質，所以成為奈米材料領域中引人注目的研究之ㄧ。然而，由於奈米材料的低穩定性，導致奈米氧化鋅在應用方面受到極大的限制。本研究著重於奈米複合材料的製備，合成奈米氧化鋅粒子使其分散於穩定之基質中，並分析其性質。
本實驗使用非離子型界面活性劑 (nonionic surfactant) 在水中形成有機模板，並以四乙氧基矽烷作為氧化矽前驅物的來源，控制四乙氧基矽烷的濃度，合成具有有序奈米孔洞 (直徑約1 - 6 nm) 的中孔洞二氧化矽。接著利用所形成的中孔洞二氧化矽作為合成奈米氧化鋅的模板，利用乙丙酮鋅作為氧化鋅前驅物，於水溶液中經過分解、過濾、氧化後，於中孔洞二氧化矽中形成奈米氧化鋅粒子。本研究藉由XRD、TEM、SEM、PL等儀器進行微結構與螢光性質的分析
實驗結果顯示：由於中孔洞二氧化矽的孔洞限制氧化鋅粒子的成長，因此所合成的氧化鋅與中孔洞二氧化矽奈米複合材料在螢光性質上和塊材氧化鋅不同，在激發光2.0電子伏特時，氧化鋅的特徵光因為量子尺寸效應而藍移到3.5電子伏特處。

Zinc oxide nanopaticles have attracted great attention because of the specific optical and electronic properties, which differ significantly from the bulk ZnO. However, the use of the ZnO nanostructures as materials is strongly restricted because of their low stability. The approach to this problem is the preparation of the so-called nanocomposite materials, namely incorporatiing ZnO nanoparticles inside a stabilizing matrix.
In this research, nonionic surfactant was used as liquid organic template and tetraethoxysilane as silica precursor to synthesis mesoporous silica with ordered arrangement nanopores (diameters are about 1 – 6 nm). The synthesized mesoporous silica could be the template to synthesize ZnO nanoparticles. We used zinc acetylacetonate to be the ZnO precursor. After reacted, filtered and oxidized, the ZnO incorporated in the mesoporous silica nanocomposite materials were formed. The results were characterized by X-ray diffraction, TEM, SEM and Photo luminescent spectrum.

總目錄
中文摘要 II
Abstract III
誌謝 IV
總目錄 V
圖目錄 VII
表目錄 IX
第一章 緒論 1
1-1 前言 1
1-2 研究目的與方向 5
第二章 理論基礎 6
2-1 中孔洞材料簡介 6
2-1-1 中孔洞材料主要研究範疇 8
2-1-2 中孔洞材料之應用 10
2-2 界面活性劑 13
2-2-1 界面活性劑的分類 13
2-2-2 微胞的形成 14
2-2-3 界面活性劑聚集體的結構 16
2-2-4 影響界面活性劑聚集體的因素 16
2-3 矽酸鹽的化學概念 17
2-4 氧化鋅發光機制 19
第三章 實驗方法與步驟 25
3-1 實驗藥品 25
3-2 實驗步驟 25
3-2-1 中孔洞氧化矽製備 25
3-2-2 於中孔洞氧化矽中合成ZnO奈米粒子 26
3-3 儀器鑑定分析 30
3-3-1 X-射線粉末繞射光譜儀 (XRD) 30
3-3-2 穿透式電子顯微鏡 (TEM) 30
3-3-3 掃描式電子顯微鏡(SEM) 31
3-3-4 氮氣等溫吸附╱脫附量測 (N2 adsorption/desorption isotherm) 31
3-3-5 紫外光-可見光光譜儀 (UV-Vis spectrum) 35
3-3-6 螢光光譜儀 (Photo luminescent spectrum) 35
第四章 結果與討論 37
4-1 氧化矽源濃度對中孔洞氧化矽之性質影響 37
4-1-1 表面形態分析 37
4-1-2 微結構分析 42
4-1-3 中孔洞二氧化矽的發光性質 50
4-2 於中孔洞氧化矽中成長奈米氧化鋅粒子之研究 54
4-2-1 微結構分析 54
4-2-2 螢光光譜與吸收光譜分析 67
第五章 結論 72
參考文獻 73




圖目錄
Fig. 1-1 The scheme of the M41S. a) MCM-41. b) MCM-48. c) MCM-50 4
Fig. 2-1 The formation route of the mesoporous molecular sieves, M41S.[14] 7
Fig. 2-2 Categories of mesoporous sieve researches 9
Fig. 2-3 The schematic of colloidal phase separation mechanism 19. 錯誤! 尚未定義書籤。
Fig. 2-3 The mechanism of micelle’s morphology. 11
Fig. 2-4 The zinc oxide band structure and exciton energy state. Eg：the energy between condution band and valence band. Ex：exciton binding energy. 22
Fig. 2-5 The Bixia Lin’s mechanism of zinc oxide vacancy energy state caculated by full-potential linear muffin-tin orbital method. 23
Fig. 2-6 K. Vanheusden’s mechanism of zinc oxide vacancy energy state. (a) In the low free carrier concentration. (b) In the high free carrier concentration. 24
Fig. 3-1 Experimental procedure of synthesizing mesoporous silica. 28
Fig. 3-2 Experimental procedure of synthesizing ZnO/mesoporous silica. 29
Fig. 3-3 (a) Types of physisorption; (b)Types of hysteresis loop 36
Fig. 4-1 The SEM micrographS of mesoporous silica at various TEOS concentration. (a) S1 (b) S2 (c) S3 (d) S4 (e) S5 (f) the magnified micrograph of S2. 40
Fig. 4-2 The small angle XRD spectrum of the mesoporous silica. (a) MS1 (b) MS2 (c) MS3 (d) MS4 (e) MS5 43
Fig. 4-3 The TEM image of the mesoporous silica. (a) MS1 (b) MS2 (c) MS3 (d) MS4 (e) MS5 47
Fig. 4-4 (a) The Nitrogen adsorption/desorption isotherm curve and (b) pore size distribution of the sample MS2 and MS5. 49
Fig 4-5 Photonluminescent spectrum (λ = 200 nm) of the mesoporous silica MS2 with its Gaussian decomposition. 51
Fig. 4-6 XRD patterns of the sample MS2-ZnO-0.005, MS2-ZnO-0.01 and MS2-ZnO-0.03. 57
Fig 4-8 TEM micrographs and EDS analysis of the sample MS2-ZnO-0.005 60
Fig 4-9 TEM micrographs and EDS analysis of the sample MS2-ZnO-0.01 61
Fig 4-10 TEM micrographs and EDS analysis of the sample MS2-ZnO-0.03 63
Fig 4-11 (a) Nitrogen adsorption/desorption isotherm curve and (b) the pore size distribution of the sample MS2, MS2-ZnO-0.005 and MS2-ZnO-0.01 64
Fig. 4-11 Photoluminescence spectra (λ = 200 nm) of the ZnO/mesoporous silica nanocomposite sample (a) MS2-ZnO-0.005 and (b) MS2-ZnO-0.01 68
Fig. 4-12 UV-Vis spectra of the sample MS2-ZnO-0.01 71








表目錄
Table 1-1 Types of pore size 3
Table 3-1 Properties of experimental raw materials. 27
Table 4-1 the sample of the mesoporous silica in the different TEOS concentration 38
Table 4-2 Schematic drawing of colloidal phase separation mechanism. 41
Table 4-3 Physical properties of mesoporous silica prepared at different silica concentration. 45
Table 4-4 The sample of the ZnO/mesoporous silica composite materials in the different Zn(acac)2 concentration. 55
Table 4-4 Texture properties of sample MS2 and nanaocomposites MS2-ZnO-0.005 and MS2-ZnO-0.01 66

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