由於奈米材料具有全新的特性，可以取代傳統材料應用在各種光電科技產品中，因此近年來成為大家努力研究的主題。早期奈米科技的研究重心在無機材料，但是有機材料具有極佳的光電特性，因此本研究以有機材料八-羥奎林鋁鹽(tris-(8-hydroxyquinolate)-aluminum, AlQ3)製備奈米粒子(零維)、奈米線(一維)與奈米結晶薄膜(二維)等有機奈米結構，研究其光電特性，並嘗試元件之製作。
本實驗使用氣相冷凝法製備AlQ3奈米結構，所得之奈米粒子呈球形，平均大小約為50~500nm，表面非常光滑類似真珠。由X光繞射(X-ray diffraction)分析發現奈米粒子為非晶(amorphous)結構。由奈米粒子的光激發光(photoluminescence, PL)光譜可以看出其發光波長範圍為4500~7000 Å，發光之中心波長為5380Å，而且當奈米粒子的尺寸變小時，其發光強度明顯增強，這是由於尺寸愈小的奈米粒子具有較大的比表面積(specific surface area)，增加了激發光源的吸收，而增加了發光強度。
AlQ3奈米線可以直接成長在矽晶圓或鍍有氧化銦錫(indium tin oxide, ITO)的玻璃基板上，奈米線的直徑約為30~50nm，長度超過1m。經由X光繞射與高解析度穿透式電子顯微鏡(high resolution transmission electron microscopy, HRTEM)分析發現奈米線為非晶結構。實驗發現AlQ3奈米線可以製備成場發射元件，其啟動電場(turn-on field)約為8.0~10.0V/m，在外加電場22V/μm時其最大電流密度約為15mA/cm2。實驗結果顯示其場發射增強因子(field enhancement factor)約為275，而且可以持續放電超過1hr，本實驗首次證實有機半導體奈米線與奈米碳管類似，均可以應用在場發射元件。
AlQ3奈米結晶薄膜直接成長在矽晶圓或鍍有氧化銦錫的玻璃基板上，其外觀為柱狀堆疊在基板表面，柱狀物的直徑約為100nm，長度為1 μm，而且其高度起伏約有100nm。實驗發現在室溫下奈米結晶薄膜之光激發光光譜具有起伏振盪的數個峰值，而且具有場發射現象，其啟動電場(turn-on field)約為12.0~15.0V/m，在外加電場22 V/μm時其最大電流密度約為0.8mA/cm2，而且可以持續放電超過0.5hr，本實驗證實有機半導體結晶薄膜與鑽石薄膜類似，均可以用來製作場發射元件。
經由傅氏轉換紅外線光譜(Fourier transfer infrared, FTIR)證實，雖然實驗所使用之製程溫度高達410°C，但是在蒸鍍的過程中AlQ3的分子鍵結並沒有被高溫破壞，顯示AlQ3分子的熱穩定性極高。而且AlQ3奈米結構可以放置在場發射電子顯微鏡(field emission gun scanning electron microscopy, FEGSEM)或是穿透式電子顯微鏡(transmission electron microscopy, TEM)中照射電子束超過3hr以上，其外觀並不會有太大的改變，顯示AlQ3奈米結構的熱穩定性，且將其放置在室溫與空氣中進行時效(aging)超過一週，發現外觀及鍵結變化不大，顯示AlQ3奈米結構確實極為安定，其未來可能的發展與應用極大。

Nanotechnology has become an important and popular research subject recently, because the quantum size effect of nano-structured materials, such as nanowires and nanoparticles, may induce new optical and electronic properties compared with those of conventional materials. Much attention is then turned to nanometer-sized organic materials due to many unique properties such as flexibility, high photoconductivity, and nonlinear optical effects that may offer novel applications in nano-optoelectronic devices. In this study, a widely-used material of organic light emitting diodes, tris-(8-hydroxyquinolate)-aluminum (AlQ3), is employed to fabricate the nanoparticles (zero dimension), nanowires (one dimension), and nanoscaled crystalline films (two dimension).
The AlQ3 nanostructures were synthesized by vapor condensation. The average sizes of the spherical nanoparticles are varying from 50 to 500 nm. The surface of the nanoparticles is quite sleek and smooth like that of pearls. The X-ray diffraction (XRD) patterns reveal that the nanoparticles have an amorphous structure. The photoluminescence spectra of the nanoparticles show a broadened peak varying from 4500 Å to 7000 Å, with the maximum intensity at about 5380 Å. The maximum intensity increases as the particle size decreases, owing to the specific surface area. The larger specific surface area of the smaller nanoparticles increases the optical absorption and further enhances the intensity of luminescence.
The AlQ3 nanowires were grown on the indium tin oxide (ITO) coated glass substrate. The diameter and length of the nanowires are about 30 to 50 nm and over 1 m, respectively. According to the XRD and high resolution transmission electron microscopy (HRTEM) analysis, the nanowires reveal an amorphous structure. The AlQ3 nanowires exhibit a low turn-on field of 8.0－10.0 V/m and a maximum current density of about 15 mA/cm2. The field enhancement factor is estimated to be 275. A stable emission current can be performed, thus the field emission of organic semiconductor nanowires was first demonstrated. It indicates that the application of this organic semiconductor in field emission is quite promising.
The nanoscaled AlQ3 crystalline film was synthesized on the ITO coated glass substrate. It was stacked with nanometer-sized rods, approximately 100 nm wide and 1 μm long, and had a surface roughness of about 100 nm. The vibronic progression with several separated peaks was observed in the photoluminescence spectrum at room temperature. It is attributed to the crystallinity of AlQ3 and the coupling of vibrations of the individual ligands to the fluorescence transition. The emission current was also observed with a turn-on field of 12.0 V/μm, and a current density of about 0.8 mA/cm2 at 22 V/μm. A stable emission current can also be performed. It demonstrates that the electrons emit from the bumps of the AlQ3 crystalline film at high voltages. Therefore, the AlQ3 crystalline film provides a new choice for field emission.
According to the Fourier transfer infrared (FTIR) spectrum, the chemical bonding of AlQ3 is preserved in the nanoparticles even after evaporation at 410°C. Moreover, all the AlQ3 nanostructures remain stable in the field emission gun scanning electron microscopy (FEGSEM) or transmission electron microscopy (TEM) for more than 3hr without any change of the surface morphology, indicating an excellent thermal stability. The chemical bonding and surface morphology of the AlQ3 nanostructures are also preserved after aging in air at room temperature for more than one week.

第一章　緒論　……………..………………………… 1
1-1 奈米科技　………………………………….……… 1
1-2 奈米材料的性質　…………………………………. 2
1-2-1 量子局限效應　………………………………..… 2
1-2-2 表面與介面效應　……………………………..… 6
1-3 實驗動機與構想　………………………………..… 7
第二章　奈米材料　……………...…………………… 9
2-1 奈米粒子　………………………………………….. 9
2-1-1 奈米粒子的製備　………………………………… 9
2-1-2 奈米粒子的成長機制　…………………………… 12
2-1-3 奈米粒子的特性與應用　………………………… 13
2-2 奈米線　……………………………………………… 15
2-2-1 奈米線的製備　……………………………………. 15
2-2-2 奈米線的成長機制　………………………………. 19
2-2-3 奈米線的特性與應用　……………………………. 20
2-2-4 有機奈米線　……………..………………………… 26
2-3 奈米碳管　……………………………………………. 28
2-3-1 奈米碳管的製備　………………………………….. 28
2-3-2 奈米碳管的成長機制　…………………………… 31
2-3-3 奈米碳管的特性與應用　………………………… 32
2-3-4 其他一維結構之奈米材料　……………………… 40
2-4 鑽石薄膜　………………………………………….. 42
2-4-1鑽石薄膜的製備　………………………………… 42
2-4-2鑽石薄膜的成長機制　…………………………… 43
2-4-3鑽石薄膜的特性與應用　………………………… 44
第三章　有機半導體　……………………..……….… 45
3-1 有機半導體　……………………………………….. 45
3-1-1 有機半導體的起源　…………….……………….. 45
3-1-2 有機半導體的發光機制　……….……………….. 46
3-1-3 有機發光二極體的發光機制　….……………….. 48
3-1-4 有機半導體的種類　…………….……………….. 55
3-2 八-羥奎林鋁鹽(AlQ3)的特性　…………………….. 58
3-2-1 分子結構　…………………….………………….. 58
3-2-2 光學性質　…………………….………………….. 60
3-2-3 電子傳輸性質　……………….………………….. 62
3-2-4 鍵結性質　…………………….………………….. 64
3-2-5 薄膜性質　…………………….………………….. 66
3-2-6 有機半導體量子井　………….………………….. 66
第四章　實驗原理與步驟　.………………..………… 69
4-1 氣相冷凝法　…………………….………………….. 69
4-1-1 氣相冷凝法的裝置　….……….………………….. 69
4-1-2 氣相冷凝法成長奈米粒子　…..………………….. 70
4-2 極化調變近場光學顯微鏡　…..…………………….. 72
4-2-1 極化調變近場光學顯微鏡量測裝置　….……….... 72
4-2-2雙色性晶體的量測　………………………………... 74
4-3 光激發光　……………………………...………….... 77
4-3-1 光激發光量測裝置　.………………...………….... 77
4-3-2 光激發光的機制　….………………...………….... 79
4-4 電子場發射　…………………………...………….... 81
4-4-1 Fowler-Nordheim方程式　…………...………….... 81
4-4-2 Fowler-Nordheim圖　………………...………….... 85
4-4-3 場發射增強係數　….………………...………….... 86
4-4-4 場發射量測裝置　….………………...………….... 86
4-5 實驗流程　………….…………………...………….... 89
4-5-1 有機半導體奈米結構製程設備　.…...………….... 89
4-5-2 試片的前處理　………….…………...………….... 90
4-5-3 AlQ3奈米結構的製備　……………...………….…. 92
4-5-3 AlQ3奈米結構的量測　……………...………….…. 96
第五章　實驗結果與討論　……………….…………. 99
5-1 AlQ3粉末　…………….……………...………….…. 99
5-1-1 粉末的外觀　…………….………………….….…. 99
5-1-2 粉末的結構　………………….…………….….…. 100
5-2 AlQ3奈米粒子　….…….……………...………….…. 101
5-2-1 奈米粒子的外觀　…………….…………….….…. 101
5-2-2 奈米粒子的結構　…………….…………….….…. 105
5-2-3 奈米粒子的成長機制　……….…………….….…. 107
5-2-4 奈米粒子的光激發光特性　….…………….….…. 108
5-2-5 以多孔性基板製備奈米粒子　.…………….….…. 110
5-3 AlQ3奈米線與奈米帶　..……………...………….…. 112
5-3-1 奈米線與奈米帶的外觀　…….…………….….…. 112
5-3-2 奈米線的結構　……………….…………….….…. 118
5-3-3 奈米線的成長機制　………….…………….….…. 121
5-3-4 奈米線的光激發光特性　…….…………….….…. 123
5-3-5 奈米線的場發射特性　……….…………….….…. 124
5-4 AlQ3奈米結晶薄膜　…...……………...………….…. 131
5-4-1 奈米結晶薄膜的外觀　…….….…………….….…. 131
5-4-2 奈米結晶薄膜的結晶特性　….…………….….…. 134
5-4-3 奈米結晶薄膜的光激發光特性　…….…….….…. 136
5-4-5 奈米結晶薄膜的場發射特性　…………….….….. 139
5-5 AlQ3奈米結構與無機奈米結構的比較　..……….…. 142
5-5-1 AlQ3奈米粒子與無機奈米粒子的比較　..….….…. 142
5-5-2 AlQ3奈米線與無機奈米線及奈米碳管的比較　…. 142
5-5-3 AlQ3奈米結晶薄膜與鑽石薄膜的比較　..….….…. 143
第六章　結論　…………………………………..…….. 144
參考文獻　……..………………………..………..…….. 146

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