發展功能性π共軛小分子之綠色合成方法學及其於太陽能電池之應用;Development of Greener Synthetic Methodologies of π-Functional Small Molecules for Solar Cell Applications

NCUIR > Engineering College > National Central University Department of Chemical & Materials Engineering > Electronic Thesis & Dissertation > Item 987654321/75822

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/75822

Title:	發展功能性π共軛小分子之綠色合成方法學及其於太陽能電池之應用;Development of Greener Synthetic Methodologies of π-Functional Small Molecules for Solar Cell Applications
Authors:	林伯翰;Lin, Po-Han
Contributors:	化學工程與材料工程學系
Keywords:	碳氫鍵芳香環化反應;染料敏化太陽能電池;有機染料分子;鈣鈦礦太陽能電池;電洞傳輸材料;Direct C-H arylation;Dye-Sensitized Solar Cell;Organic Sensitizers;Perovskite Solar Cell;Hole Transporting Materials
Date:	2018-01-30
Issue Date:	2018-04-13 10:48:40 (UTC+8)
Publisher:	國立中央大學
Abstract:	有機半導體材料的合成方法，現階段還是依賴傳統的人名反應，本文中第一部份我們將介紹一個具有原子及步驟經濟的合成方法，可以從傳統的人名反應所需要的六步縮短至兩步來製備D-A-π-A型的有機染料分子。在我們提出的合成方法學中，將以thieno[3,4-c]pyrrole-4,6-dione (TPD)為核心，接上各種推電子基團(Donor)、拉電子基團(Acceptor)以測試該反應條件的廣度。本文最後也將合成到的有機染料CYL-3、CYL-4實際應用於染料敏化太陽能電池(DSSCs)並測得其能源轉換效率(PCE)為4.76-6.02 %。第二部份，我們將介紹一個靈活的合成策略去製備D-π-A-π-D型的對稱分子，在我們的合成條件下，對稱的小分子有機半導體具有從核心(core)出發或者從末端基出發的兩種途徑可供選擇。最後，我們利用可以再減少純化步驟的一鍋化(one-pot)策略並結合我們的條件去製備D-π-A-π-D型的有機光電材料，而整體產率達到30~40 %。也證明我們提出的條件是具有步驟經濟、對環境友善、純化步驟少的一個好途徑。第三部份，我們發表了以thieno-isoindigo (TII)為中間核心並搭配一鍋化 (one-pot)的實驗步驟來合成D-π-A及D-π-D型的有機光電材料，先經由實驗條件的最佳化測試之後，再利用該方法合成一系列的電洞傳導材料(Hole Transporting Materials)，而利用我們提出來的方法，不對稱的電洞傳導材料可達到40~80 %的產率，而對稱的電洞傳導材料在相同條件下也可以達到40~50 %的產率，最後我們將一系列的電洞傳導材料應用於鈣鈦礦太陽能電池中。最後，以spiro-fluorene為核心的電洞傳導材料並應用於鈣鈦礦太陽能電池一直有非常高的效率表現，其中最熱門的SpiroOMeTAD到目前為止更是許多科學家想要超越的目標之一。而本部份的工作同樣以spiro-fluorene為核心，設計一系列的電洞傳輸材料，其中Spiro-tBuFET實際應用於鈣鈦礦太陽能電池中，創造出高達17 %的光電轉換效率，而且還具有非常優異的穩定性，太陽能電池元件在存放四週後，依然保有5 %的光電轉換效率。 ;Over the past decade, Pd-catalyzed direct C-H arylations have undergone intensive development. Compare some traditional cross-coupling reactions with direct C-H arylations, the latter has advantages of atom economy and low cost. But the synthetic pathway of organic photoelectric materials still relies on traditional cross-coupling reactions. Hence, we reported a series of π-conjugated molecules which are prepared by Pd-catalyzed direct C-H arylations. First, we reported a series of unsymmetrical D–A–π–A type organic sensitizers which are synthesized by our optimum conditions. Particularly, the reaction step can be decreased from traditional six steps to two steps. Based on our synthetic study, DSSCs are fabricated and characterized using two designed sensitizers. The photovoltaic characterization of the devices affords an open-circuit voltage of 0.60–0.69 V, a short-circuit current density of 10.85–11.07 mA/cm2, and a fill factor of 69.9–70.8 %, which corresponds to an overall power conversion efficiency of 4.61–5.33 %. Second, it’s very common to see D-π-A-π-D type organic photoelectric materials which are used in OPV or OFET. In this work, we demonstrate Pd-catalyzed direct C-H arylations to obtain D-π-A-π-D type molecules. Besides, this methodology has shown that two different pathways (from core structure and from end structure) to access target molecules. Third, a new D-π-A and D-A-D type Hole Transporting Materials (HTMs) incorporating thienoisoindigo (TII) as the central core, triphenylamine as the donor, dicyanovinylene and 2-ethylhexyl cyanoacetate as the terminal acceptor was prepared. Furthermore, D-π-A type products can be prepared by our one-pot direct C-H arylation. Thus, the perovskite solar cell (PSC) based on symmetrical HTM with four methoxyl groups gave an overall power conversion efficiency of 10.8 %. Five novel spiro-fluorene based HTMs were designed and synthesized by direct C-H arylations. Compare to Spiro-OMeTAD, the Spiro-tBuFET was incorporated into perovskite solar cell which shows an excellent overall power conversion efficiency of 17.45 % without oxidation process. Based on our synthetic approach and the performance of PSC, it has indicated that the Spiro-tBuFET has enormous potential to replace Spiro-OMeTAD.
Appears in Collections:	[National Central University Department of Chemical & Materials Engineering] Electronic Thesis & Dissertation

Files in This Item:

File	Description	Size	Format
index.html		0Kb	HTML	364	View/Open

社群 sharing

Loading...