- 學位論文
合成與評估具有不同外圍基團及核心金屬之新型酞菁作為鈣鈦礦太陽能電池之無添加電洞傳輸材料研究
Synthesis and Evaluation of New Phthalocyanines with Various Peripheral Groups and Core Metals as Dopant-Free Hole Transporting Materials for Perovskite Solar Cells
摘要
摘要 於先前文獻報導中，酞菁(Phthalocyanine, Pc)具有良好的熱、化學穩定性、高電荷傳輸效率、易於調整的能階和外圍取代基，且其環中空腔具有與多達70種金屬形成配位化合物的特性，使酞菁於鈣鈦礦太陽能電池之電洞傳輸層受到青睞。 本篇論文中，藉由具延伸特性的官能基，合成了四種以酞菁為主體的衍伸物。分別於酞菁外圍接上不同取代基，以及不同的中心金屬，命名為ZnCOPc、CuCOPc、ZnCNPc以及CuCNPc。於分子設計中，引入鈍化鈣鈦礦層的想法，在外圍取代基上設計具有孤對電子的氧或氮，與鈣鈦礦層未配位的鉛離子進行配位降低缺陷。大型的苯氧基團能夠提供酞菁分子良好的溶解度，使新型酞菁分子能夠於溶液製程中使用。新型的酞菁分子於紫外-可見光吸收光譜中，均於670 nm處(Q band)以及350 nm處(B band)發現典型的酞菁峰。藉由計算莫耳消光係數(ε)可得知，相同官能基下中心金屬為鋅取代的酞菁具有比銅取代高的莫耳消光係數，因鋅離子具有閉合殼層(close-shell)特性，因此莫耳吸收度較銅離子酞菁高。額外的光子吸收能夠提升鈣鈦礦太陽能電池光電轉換效率。最後由電化學之循環伏安計算其HOMO、LUMO能階，四種新型酞菁分子均符合於鈣鈦礦太陽能元件電洞傳輸層之需要，具有較高的HOMO及LUMO能夠提供電洞轉移並阻擋電子轉移。
並列摘要
Abstract Based on previous literature reviews, phthalocyanine (Pc) has been recognized for its good thermal, and chemical stability, high charge mobility, tunable energy level, and peripheral groups as well as its macrocyclic coordination complexes with up to 70 types of metals. Phthalocyanine has been well applied as the hole transport material (HTM) of perovskite solar cells. In this work, we synthetized four phthalocyanine-based HTM through applying functional groups with extended characteristics. Various peripheral groups and core metals for the phthalocyanine-based HTMs, namely ZnCOPc, CuCOPc, ZnCNPc and CuCNPc, are synthesized. In the molecular design, ideas of passivate perovskite layer were introduced. Oxygen or nitrogen with lone-pair electrons are designed on the peripheral groups to coordinate with the uncoordinated Pb2+ on the perovskite film surface to passivate defects. The phenoxy group provides good solubility of phthalocyanine molecules, and enables the use of new phthalocyanine compound in solution processing. Representative phthalocyanine peaks are found at 670 nm (Q band) and 350 nm (B band) in the UV-visible absorption spectra of the new phthalocyanine compound. From the molar extinction coefficient (ε) measurements in the same functional groups, the zinc phthalocyanines exhibit higher ε than that of the copper phthalocyanines. This is because the Zn2+ has a closed-shell characteristics, so that molar extinction coefficient is higher than copper phthalocyanine. Extra photon absorption can improve the power conversion efficiency of perovskite solar cells. Finally, the new phthalocyanine compound energy levels were calculated by electrochemical cyclic voltammetry. The four new phthalocyanine compound all meet the needs of the hole transport materials of PSCs. The higher HOMO and LUMO could facilitate the hole transfer but block electron transfer.