當圓形或球形腔體有較高折射率時，光可藉由全反射的方式不斷的在腔體內傳遞並在特定波長下產生駐波，此現象稱為耳語廊模態。金與空氣介面可存在表面電漿波，但其波向量大於同頻率之自由電磁波，因此只有在滿足相位匹配 (動量守恆)之條件下，才能產生耦合。當球狀耳語廊共振腔被放置於金基板上時，模態將根據其偏振方向及繞轉方位之不同，在接觸點附近透過近場漸逝波與基板產生不同的交互作用。本研究主要是研究單晶金基板對自組裝有機共軛高分子螢光微米球內之耳語廊模態的影響，包含對光譜尖峰強度及位移的影響。
本研究獲致兩項結論：(1)強度方面，我們發現磁橫波耳語廊模態 (TM mode)會經由奧圖組態 (Otto configuration)耦合成金板表上的電漿波而離開共振腔，這使得光譜中相對應尖峰之強度下降。(2)光譜位移方面，我們實驗觀察到金基板使電橫波耳語廊模態 (TE mode)藍移，TM mode紅移，經由理論分析，我們將此歸因於金板對電橫波及磁橫波分別產生正及負的古斯-漢欣位移 (Goos-Hänchen shift)，等同於球狀腔體圓周分別會等效縮小及放大，因此光譜尖峰分別產生藍位移及紅位移。以往僅能使用理論計算來比對標示的光譜尖峰值所對應的TE mode及TM mode，此研究顯示，亦可利用觀測其金屬表面電漿耦合以及古斯-漢欣位移兩種方式，在實驗上分辨出兩種模態。
最後，本論文也對石墨烯基板對耳語廊模態之影響做了初步探討。由於已知石墨烯對近距離偶極光源(dipole source)之消光(quenching)取決於偶極方向，偶極平行於石墨烯平面則消光效應大，反之則小。因此我們希望了解石墨烯基板對TE mode及TM mode耳語廊模態是否也具類似的消光差異。目前初步結果顯示並無觀測得到之消光差異，原因可能是因為石墨烯對偶及光源的消光機制主要為電子轉移及福斯泰能量轉移(Förster resonance energy transfer, FRET)，石墨烯與耳語廊模態耦合機制明顯不同，因此沒有相似消光差異。關於石墨烯與耳語廊模態耦合機制的研究，未來仍需要更多實驗與理論計算。

Light can be totally internally reflected inside a sphere made of dielectric material with refractive index higher than the environment. At specific wavelengths, standing waves are established, forming the photonic whispering-gallery modes (WGMs). On the interface of air and gold, surface plasmons (SPs) can be excited by photons if the momentum matching condition is fulfilled. When the spherical WGM resonator is placed on the gold substrate, the evanescent near fields of the WGMs can interact with the gold substrate. Depending on the polarization and the orbiting orientation of the WGMs, the interaction can result in spectral shift and intensity variation. The influence of the gold substrate on the WGM is of fundamental interest and practical importance when the sphere is to be connected to metallic electrodes for photoelectric effects. In this thesis, we investigate the influence of single-crystalline gold substrate on the WGMs of self-assembled semiconducting fluorescent π-conjugated polymer microspheres. In particular, we focus on the effects on WGM peak intensity and spectral shift. For peak intensity, we found that all peaks and the broadband fluorescence background in the emission spectrum are enhanced by the gold substrate. However, the intensity of transverse magnetic (TM) WGMs is usually lower than the corresponding transverse electric (TE) modes. This is found to stem from the WGM-to-SP coupling of the TM modes via Otto configuration. As for the spectral shift, we have observed that gold substrate results in blue shift of TE modes and red shift of TM modes. While for ITO substrate, both TE and TM show red shift. With theoretical and numerical analysis, we attribute the red and blue shift of the TM and TE mode to the negative and positive Goos-Hänchen shift on the gold substrate, respectively. The negative and positive Goos-Hänchen shifts correspond to effective enlargement and shrinkage of the sphere circumference and thus the red-shifted and blue-shifted peak positions, respectively. Typically, the assignment of TE and TM modes relies on theoretical analysis. This study shows that by identifying the metal surface plasmon coupling effect and the Goos-Hänchen shifts, the assignment of TE and TM mode can also be done experimentally.
Finally, the influence of the graphene substrate on the whispering gallery mode is discussed. Graphene is known to be an efficient quencher and the quenching effect depends on the dipole orientation with respect to the graphene surface. Dipoles parallel to the graphene plane are quenched much more effectively than those perpendicular to the surface. Therefore, it is interesting to know if graphene substrate has different quenching effects on the TE and TM modes. The preliminary results show that there is no observable difference. This might be due to the fact that the coupling of WGMs to graphene substrate is different from that of dipole sources to graphene. The details of the influence of graphene on WGMs require further experimental and theoretical works.

第1章 原理 1
1.1 半導體共軛高分子 1
1.1.1 共軛高分子 1
1.1.2 螢光放光 2
1.1.3 有機半導體雷射 4
1.2 耳語廊模態 5
1.2.1 光在介電質球中傳遞 6
1.2.2 耳語廊模態特徵頻率 11
1.3 古斯－漢欣位移 13
1.4 表面電漿子 16
1.4.1 電磁波的傳遞 17
1.4.2 金屬表面電漿子模式 19
1.4.3 激發表面電漿子 23
第2章 實驗架設與步驟 26
2.1 模擬架設 26
2.1.1 時域有限差分法 26
2.1.2 模擬設定 26
2.1.3 耳語廊模態共振光譜 28
2.1.4 耳語廊模態共振電場圖 30
2.1.5 耳語廊模態電場傳遞 31
2.2 樣品合成及光學架設 33
2.2.1 螢光微米球合成方法 33
2.2.2 單晶金片合成 34
2.2.3 樣品製備 36
2.2.4 奈米棋盤格及圓環結構 38
2.2.5 單層石墨烯製備 38
2.2.6 光學架設 41
第3章 實驗結果與討論 44
3.1 螢光增益 44
3.2 基板對螢光微米球內耳語廊模態之影響 47
3.2.1 耳語廊模態實驗及模擬光譜 47
3.2.2 耳語廊模態電場圖 50
3.2.3 耳語廊模態電場傳遞 52
3.2.4 耳語廊模態實驗結果 55
3.3 耳語廊模態產生之表面電漿波 60
3.4 基板對耳語廊模態之光譜位移 63
3.5 石墨烯對耳語廊模態之影響 68
第4章 結論與未來展望 70
參考文獻 72

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