以不同的連結基及不同的推電子基修飾NMFP，設計出不同的電子受體分子，接著利用理論計算的方法分析他們的相關性質，如能隙、光譜…等，研究連結基與推電子基對分子造成的影響，試圖找出具有高LUMO值或低能隙的電子受體，以提升BHJ太陽能電池的光電轉換效率。
  結果發現，連結基有助分子形成電荷分離狀態，長度愈長時，HOMO愈高，能隙愈低，但LUMO也下降；S0→S1的躍遷主要發生在HOMO、LUMO間，最大吸收波長有紅位移的現象，且吸收波長範圍分布廣泛。
  預期NMFP-L1和NMFP-L3具有比較好的發展潛力，所以選擇此二系列結合不同的推電子基，做進一步分析；NMFP-L1和NMFP-L3與推電子基的結合後，最大吸收波長有紅位移的現象；八個分子中，N-L3-D1的平面性最好；LUMO值最高的是N-L3-D2，能隙值最小的是N-L1-D4，整體數值都不錯的是N-L1-D2。

In this study, NMFP has been modified by different linkers and electron-donating groups to design a series of electron acceptor for BHJ (Bulk Heterojunction) solar cell fabrication. The optoelectronic properties of these designed electron acceptor, like band gap and UV-Vis spectra et al, have been characterized according to theoretically calculation. The effects from linkers and electron-donating groups to electron acceptor have been studied to design the electron acceptor of high LUMO (Lowest Unoccupied Molecular Orbital) or low band gap for enhancement of the efficiency of BHJ solar cell.
  The results have demonstrated the linker with higher chain length has higher HOMO and the lower LUMO. Thus the Eg energy level has been also decreased. Due to the decreasing of Eg energy level, the major molecular orbital contribution of S0 to S1 was concentrated on the HOMO to LUMO transition. Compare to the compounds without linker modification, red shift and broadening of absorbance have been observed in the spectra of those electron acceptor modified by the designed linkers.
  NMFP-L1 and NMFP-L3 are expected that they are suitable for developing so they were picked to be analyzed more. After combining with electron donors, the largest absorbed wavelengths of NMFP-L1 and NMFP-L3 had red shifts. Among these eight compounds, the surface of N-L3-D1 was the most planar, N-L3-D2 had the highest LUMO, N-L1-D4 had the lowest Eg, and N-L1-D2 was fine generally.

中文摘要 I
英文摘要 II
目錄 III
表目錄 V
圖目錄 VI
第一章 緒論 1
1-1 太陽能電池簡介 1
1-2 電子予體-受體異質接面太陽能電池 10
 1-2.1 單層結構 12
 1-2.2 雙層異質接面結構 12
 1-2.3 單層異質接面結構 (Bulk Heterojuntion, BHJ) 13
 1-3 影響BHJ太陽能電池效能之因素 15
 1-4 文獻回顧 17
1-5 研究動機 21
第二章 原理與方法 23
2-1 理論計算 23
2-2 量子化學 24
 2-2.1 薛丁格方程式 25
 2-2.2 原子單位 26
 2-2.3 波恩－歐本海莫近似法 27
2-3 計算方法－量子近似法 29
 2-3.1 Hartree－Fock方程式 29
 2-3.2 密度泛函數理論 33
 2-3.3 半經驗計算方法 37
 2-3.4 基底函數組 41
 2-3.5 SIESTA介紹 45
第三章 研究設備 50
3-1 影體設備 50
3-2 軟體設備 52
第四章 結果與討論 53
4-1 NMFP與PCBM分子之設計 56
4-2 NMFP與連結基結合後的分子構形 58
4-3 NMFP-Linker分子的HOMO、LUMO與能隙分析 63
4-4 NMFP-Linker的光譜分析 66
4-5 將結合連結基的NMFP再接上推電子基 73
 4-5.1 NMFP與連結基、推電子基結合後的分子構形 75
 4-5.2 NMFP-Linker-Donor分子的能隙分析 77
 4-5.3 NMFP-Linker-Donor分子的光譜分析 78
 4-5.4 結論 82
第五章 結論 83
第六章 參考文獻 85

表 目 錄    頁次
表2-1半經驗法的發展過程40
表4-1 NMFP-L1的鍵長61
表4-2 NMFP-L1~4 n=4 連結基內部的鍵長62
表4-3 NMFP-L1與NMFP-L2的HOMO、LUMO與能隙數值63
表4-4 NMFP-L3與NMFP-L4的HOMO、LUMO與能隙數值65
表4-5 NMFP-L3的吸收光譜66
表4-6 NMFP-L3的HOMO與LUMO電子雲分佈比例67
表4-7 NMFP-L1~L4 n＝3的光譜數據69
表4-8 NMFP-L1~L4 n＝3的HOMO與LUMO電子雲分佈比例71
表4-9 N-L1-與N-L3-D1~D4的鍵長76
表4-10 N-L1-與N-L3-D1~D4的兩面角76
表4-11 N-L1-與N-L3-D1~D4的能隙數據77
表4-12 N-L1-與N-L3-D1~D4的光譜數據79
表4-13 N-L1-與N-L3-D1~D4的HOMO與LUMO電子雲分佈比例80
圖 目 錄    頁次
圖1-1路竹示範場的自動追日功能高聚光太陽能面板4
圖1-2太陽能電池發電原理示意圖6
圖1-3電子予體－受體異質接面太陽能電池元件原理示意圖7
圖1-4可饒曲式有機太陽能電池原型9
圖1-5 P3HT、MDMO-PPV與PCBM結構示意圖10
圖1-6雙層異質接面太陽能電池示意圖11
圖1-7可撓式的有機高分子太陽能電池元件示意圖11
圖1-8早期的有機太陽能電池元件之單層結構12
圖1-9電子予體/ 受體之雙層異質接面結構12
圖1-10有機高分子電子予體/ 受體太陽能電池13
圖1-11電子予體/ 受體的單層異質接面結構13
圖1-12 BHJ單層異質接面元件示意圖14
圖1-13太陽能電池電流電壓關係圖15
圖1-14 VOC和HOMO、LUMO關係的示意圖17
圖1-15 NMFP結構圖19
圖2-1不同基底函數與1s軌域的Slater函數近似程度42
圖2-2對於極性分子系統的軌域型態，用加入額外軌域型態函數來加以修正（p軌域加上d函數；s軌域加上p函數）44
圖2-3氧原子的虛原子軌域47
圖2-4平面波基函數與軌域基函數對計算總能量收歛比較圖49
圖2-5在不同基函數計算總能量與晶格常數變化圖49
圖4-1以HyperChem 7.5做分子初始結構的建構54
圖4-2以SIESTA 2.0做幾何結構的最佳化54
圖4-3.1以Gaussian 03做TDDFT和POP的計算55
圖4-3.2以UltraEdit-32做細部的設定55
圖4-4 MDMO-PPV、PCBM及NMFP之HOMO、LUMO比較圖57
圖4-5 NMFP與連結基結合的示意圖58
圖4-6 L1、L2、L3及L4的取代基結構圖58
圖4-7 NMFP-L1的分子構形59
圖4-8以NMFP-L1的n=2為例，鍵長與兩面角的命名60
圖4-9 NMFP-L3 n＝1~5的MO圖67
圖4-10 NMFP-L3 n＝1~5的DOS分布圖68
圖4-11 NMFP-L1~L4 n＝3的MO圖70
圖4-12 NMFP-L1~L4 n＝3的DOS分布圖71
圖4-13 NMFP-Linker-Donor 示意圖73
圖4-14四種不同的推電子基74
圖4-15 N-L1-D1~D4  75
圖4-16 N-L3-D1~D4  75
圖4-17 N-L1-與N-L3-D1~D4的MO圖80
圖4-18 N-L1-與N-L3-D1~D4的DOS圖81

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