半導體奈米材料之合成與特性分析及其應用

Abstract

本篇研究主要在探討半導體奈米粒子之合成與應用，分為兩部分。第一部分 ，利用具有苯胺基官能化之poly[(4,4'-bis(2-ethylhexyl) -dithieno [3,2-b:2',3'-d]silole) -2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT-NH2)，其尾端的胺基可附著於碲化鎘（CdTe）奈米粒子的表面，另一方面，藉由以苯硫醇（benzene-1,3-dithiol）作為溶劑蒸氣再結晶輔以加熱退火處理，以增進於施體（donor）與受體（acceptor）之介面的電荷分離，而使得電荷有效地傳遞，如此可達到增加hybrid太陽能電池效率之目的，元件效率可達3.2%。第二部分，在一鍋化合成法下，藉由界面活性劑油胺（oleylamine）的注入促使市售低毒性的前驅物，包含氯化銅（CuI）、醋酸銦（In(CH3COO)3）、二乙基二硫胺基甲酸鋅（Zn(S2CNEt2)2）等進行反應，合成出具有放光強度高的(ZnS)x-Cu0.1InS1.55(ZCIS)/ZnS核殼奈米粒子。在反應過程中，ZCIS核可長時間（≥ 60 min）維持組成均勻性與類似的光學性質，因此可接續進行陽離子交換而形成ZnS殼。所合成出的核殼奈米粒子具有超過40%以上的量子效率，並且可藉由控制組成的成分導致放光由綠色變成紅色。此外，藉由界面活性劑誘使之一鍋化反應可達到量產的目的。在單次反應下，已成功地分別合成出1.6 g的綠色、2.27 g的黃色和2.52 g的紅色之ZCIS/ZnS奈米粒子。

Herein, the main theme of our study focuses in two parts as follows. First, a record high PCE of up to 3.2% demonstrates that the efficiency of hybrid solar cells (HSCs) can be boosted by utilizing a unique mono-aniline end group of poly[(4,4'-bis(2- ethylhexyl)-dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT-NH2) as a strong anchor to attach to CdTe nanocrystal surfaces and by simultaneously exploiting benzene-1,3-dithiol solvent-vapor annealing to improve the charge separation at the donor/acceptor interface, which leads to efficient charge transportation in the HSCs. Second, a method lying addition of oleylamine ligand to trigger the reaction for synthesis of highly emissive (ZnS)x-Cu0.1InS1.55(ZCIS)/ZnS core/shell NCs in one-pot reaction is developed using the low toxic and commercial precursors (CuI, In(CH3COO)3, Zn(S2CNEt2)2). The as-prepared ZCIS core is able to maintain the compositional homogeneity and similar optical properties during a long period of reaction time (≥ 60 min), so that subsequent cationic exchange can be carried out to form the ZnS shell. The resulting core/shell NCs exhibit high quantum yield (> 40%) and emission is tunable from green to red depending on elemental composition. This surfactant induced one-pot reaction also offers scale-up advantage, with 1.6 (green), 2.27 (yellow) and 2.52 (red) grams per reaction being successfully made.