合成含喹啉衍生物非對稱方酸染料應用於染料敏化太陽能電池

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洪瑋辰(Wei-chen Hong) 查詢紙本館藏

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化學學系

論文名稱

合成含喹啉衍生物非對稱方酸染料應用於染料敏化太陽能電池
(Synthesis of Unsymmetrical Quinoline-Based Squaraine Dyes for Panchromatic Dye-Sensitized Solar Cells)

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★ 合成新穎輔助配位基於無硫氰酸釕金屬光敏劑在染料敏化太陽能電池上的應用	★ Design and Synthesis of Ruthenium Dyes for High Open-circuit Voltage Dye-sensitized Solar Cells

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摘要(中)

由於石化能源所造成的環境問題成為注目的焦點，使得尋找替代能源成為目前的重要課題之一，利用太陽能電池將光能轉換成電能為目前的熱門研究。染料敏化太陽能電池 (dye-sensitized solar cell, DSSC)具有透光性、可撓曲性及低製造成本等優點，是目前主要的研究領域之一。釕金屬錯合物是常見用於DSSC的高效率染料，但釕金屬錯合物染料無法有效吸收遠紅光(far-red (FR))及近紅外光區(near-infrared (NIR))區域的光子，為了進一步提高DSSC的光電轉換效率，發展FR/NIR染料是相當重要的工作。本論文設計合成具有高吸收係數和吸收涵蓋FR/NIR區的squaraine染料分子，採用donor-π-conjugated-acceptor的設計概念，以triphenylamine為donor，用具推電子能力的EDOT作為共軛片段，使用quinoline做為連接squaraine與羧酸基的延長共軛單元，合成出不對稱的染料WCH-SQ10及WCH-SQ11，這兩個 squaraine 光敏化劑之最大吸收波長分別為 686 nm和 673 nm，吸收係數為 92376 M-1 cm-1和87154 M-1 cm-1，半高寬為122和120 nm，以這兩個染料所組裝成的DSSC元件之光電轉換效率分別為1.77 % (Jsc = 9.25 mA/cm2，Voc = 374 mV，FF = 0.51)和1.96 % (Jsc = 9.06 mA/cm2，Voc = 391 mV，FF = 0.55)。元件的IPCE圖顯示使用WCH-SQ10及WCH-SQ11為染料之DSSC在波長800-1100 nm範圍內還有IPCE值，顯示含squaraine之染料做為FR/NIR之潛力。

摘要(英)

The environmental problems related to the fossil energy is one of the energy issues causing great attention. Alternative energy sources becomes one of the important subject people are searching for. Solar cell, which converts light energy into electricity, is the most promising technology amongst the renewable energy. Dye-sensitized solar cell, DSSC, is considered as an alternative to the conventional solar cells due to its transparence, flexibility, high conversion efficiency, and low cost. Ruthenium complexes exhibit relatively high DSSC performance. However, ruthenium complexes did not efficiently absorb the photons in the Far-Red (FR)/Near-Infrared (NIR) region. To improve the performances of DSSCs, it would be essential to develop FR/NIR sensitizer. In this thesis, we designed and synthesized two new donor-π-conjugated-acceptor (D-π-A) unsymmetrical squaraine dyes, WCH-SQ10 and WCH-SQ11. These two squaraine dyes, have a triphenylamine as an electron donor, 3,4-Ethylenedioxythiophene as a conjugate moiety, and quinoline with COOH as an acceptor. WCH-SQ10 showed absorption maximum (λmax) centered at 686 nm with a molar absorption coefficient (ε) of 92376 M-1 cm-1 and λmax of WCH-SQ11 centerd at 673 nm with a ε of 87154 M-1 cm-1. The full width at half-maximum (FWHM) are 122 nm and 120 nm for WCH-SQ10 and WCH-SQ11, respectively. The overall conversion efficiency (ŋ) for WCH-SQ10 was 1.77 % (Jsc = 9.25 mA/cm2，Voc = 374 mV，FF = 0.51), for WCH-SQ11 was 1.96 % (Jsc = 9.06 mA/cm2，Voc = 391 mV，FF = 0.55) under the illumination of AM (air mass) 1.5 global simulated sunlight (100 mW/cm2). Incident photon-to-current conversion efficiency (IPCE) spectra of the devices sensitized by WCH-SQ10 and WCH-SQ11, reveal the efficiency at wavelength from 800 nm to 1100 nm. The results suggest that squaraine dye is a promising FR/NIR sensitizer.

關鍵字(中)

★ 方酸
★ 染料敏化太陽能電池

關鍵字(英)

★ Squaraine Dyes
★ Panchromatic
★ Dye-Sensitized Solar Cells

論文目次

摘要……………………………………………………………..i
Abstract …………………………………………………..…...ii
謝誌............................................................................................iii
目錄..…………………………………………………………..iv
圖目錄…………………………………………………………ix
表目錄 ………………………………………………………xiv
附錄...........................................................................................xv
第一章序論……………………………………………………………1
1-1 太陽能簡介 ………………………………………………………...1
1-2 太陽能電池的種類 ………………………………………………...3
1-3 染料敏化太陽能電池……………………………………………….4
1-4 染料敏化太陽能電池的組成和工作原理………………………….5
1-5 光電轉換效率( ŋ )的量測 …………………………………………7
1-6 IPCE（incident photon to current conversion efficiency）…………8
1-6-1 總光電轉換效率……………………………………………...9
1-7 光敏化劑-染料…………………………………………………….10
1-7-1 有機染料(Metal-Free Organic Dyes)………………………..11
1-7-2近紅外光染料 (Near-IR Dyes) ……………………………...18
1-8 研究動機…………………………………………………………...30
第二章實驗部分……………………………………………………32
2-1 實驗藥品…………………………………………………………...32
2-2 儀器分析與樣品製備……………………………………………...36
2-2-1紫外光/可見光及近紅外光吸收光譜儀；Ultraviolet/
Visible and Near-Infrared Absorption Spectroscopy
(Cary 300 UV/Vis Spectrometer)...............................................36
2-2-2螢光光譜儀；Emission Spectroscopy (FluoroMax-4
spectro- fluorometer (HORIBA JOBIN YVON))................37
2-2-3紅外光吸收光譜儀；Infrared Absorption Spectroscopy
(Bio-rad FTS-155，FT-IR Spectrometer).................................38
2-2-4液態核磁共振光譜儀；Solution State Nuclear
Magnetic Resonance Spectrometer (Bruker
DRX-300 MHz、Bruker DRX-500 MHz)…………………...38
2-2-5 Electrochemical Measurement；電化學測量裝置
(AUTOLAB PGSTAT30 電流/電位儀) …………………….39
2-2-6理論計算方法；Time-dependent Density Function
Theory, TD-DET ……………………………………………..40
2-2-7元件組裝與測試 …………………………………………….40
2-2-8電化學交流阻抗光譜；electrochemical impedance
spectroscopy, EIS……………………………………………..40
2-3 染料合成步驟 …………………………………………………...41
2-3-1 (E)-3- [[[3-(5-(4-(bis(4-(hexyloxy)phenyl)amino)phenyl)
-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-hydroxy-4-
oxo-2-cyclobuten-1-yl- diene]methyl]1-methyl-3H-
quinaldinium iodide -6-yl] acrylic acid , WCH-SQ10
之合成 ......................................................................................41
2-3-2 6-Carboxy-2-[[3-(5-(4-(bis(4-(hexyloxy)phenyl)amino)
phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-
hydroxy-4-oxo-2-cyclobuten-1-yl-diene]methyl]-1-
methyl-3H-quinolium iodide , WCH-SQ11之合成 ..............43
2-4 合成步驟 ........................................................................................46
2-4-1 3,4-dichloro-3-cyclobutene-1,2-dione (簡稱SQ-Cl2)
之合成.....................................................................................47
2-4-2 1-hexyloxyl-4-iodobenzene (簡稱h-IB)之合成...................48
2-4-3 N, N-Bis(4-hexyloxyphenyl)-4-bromophenylamine
(簡稱Br-TPA- Oh)之合成......................................................49
2-4-4 2-{4-[N,N-Bis(4-hexyloxyphenyl)amino]phenyl}-
3,4-(ethyl-enedi- oxy) thiophene (簡稱EDOT-TPA
-Oh)之合成 ...........................................................................50
2-4-5 3-(5-(4-(bis(4-(hexyloxy)phenyl)amino)phenyl)-2,3
-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-4-chlorocyclobut
-3-ene-1,2-dione (簡稱Cl-SQ- EDOT-TPA-Oh)之合成......51
2-4-6 3-(5-(4-(bis(4-(hexyloxy)phenyl)amino)phenyl)-2,3
-dihydro-thieno[3,4-b][1,4]dioxin-7-yl)-4-
hydroxycyclobut-3-ene-1,2-dione (簡稱OH -SQ -EDOT-
TPA-Oh)之合成 .....................................................................52
2-4-7 (E)-methyl 3-(2-methylquinolin-6-yl)acrylate (簡稱
Ae-MQ)之合成........................................................................53
2-4-8 (E)-3-(2-methylquinolin-6-yl)acrylic acid (簡稱Aa-
MQ)之合成 ............................................................................53
2-4-9 (E)-3-(2-methyl-1-methyl-3H-quinaldinium iodide
-6-yl) acrylic acid (簡稱Aa-MQ-m)之合成...........................54
2-4-10 (E)-3- [[[3-(5-(4-(bis(4-(hexyloxy)phenyl)amino)
phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-
hydroxy-4-oxo-2-cyclobuten-1-yl-diene]methyl]1-
methyl-3H-quinaldinium iodide -6-yl] acrylic acid ,
WCH-SQ10之合成...............................................................55
2-4-11 2-methylquinoline-6-carbaldehyde (簡稱MQ-A) 之
合成………………………………………………………..56
2-4-12 2-methylquinoline-6-carboxylic acid (簡稱MQ-acid)
之合成 ……………………………………………………57
2-4-13 6-Carboxy-2-methyl-1-methyl-3H-quinolium iodide
(簡稱MQ-acid-m)之合成…………………………………58
2-4-14 6-Carboxy-2-[[3-(5-(4-(bis(4-(hexyloxy)phenyl)amino)
phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-
hydroxy-4-oxo-2-cyclobuten-1-yl-diene]methyl]-1-methyl
-3H-quinolium iodide , WCH-SQ11之合成..........................58
第三章結果與討論………………………………………………...61
3-1 WCH-SQ10和WCH-SQ11的合成探討 ……………………61
3-2 WCH-SQ10及WCH-SQ11的光學性質探討和邊界
軌域(frontier orbitals)分佈之理論計算結果…………………62
3-3 WCH-SQ10及WCH-SQ11邊界軌域(frontier orbitals)
之能階位置 …………………………………………………..71
3-4 染料分子WCH-SQ10、WCH-SQ11與JYL-SQ5所組裝
成之電池元件的效率及性質探討 …………………………..75
第四章結論…………………………………………………..85
第五章參考文獻 ……………………………………………87

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指導教授

吳春桂(Chun-guey Wu)

審核日期

2012-7-26

推文