PUKYONG

Synthesis and Characterization of Conjugated Copolymers with Fluorinated Quinoxaline for Polymer Solar Cells

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Alternative Title
고분자 태양전지에 사용되는 플로로기를 도입한 퀴녹살린을 포함하는 공액고분자의 합성과 특성
Abstract
전 세계적인 에너지 고갈과 환경오염 문제로 친환경 재생에너지의 개발이 활발하게 이루어지고 있는 가운데, 태양을 이용한 대체에너지는 특히 각광받고 있다. 태양은 친 환경적이고 전 세계 어디에서나 접근이 용이하며 에너지의 양이 무한하다는 점 에서 많은 연구가 이루어지고 있다. 기존의 무기계 실리콘을 이용한 태양전지는 그 재료비용과 제조비용이 비싸 경제적으로 어려움이 많다. 이러한 문제를 해결하기 위해 저 가격의 태양전지가 요구되었고, 전도성고분자를 이용한 유기태양전지는 저 가격 대면적의 용액공정으로 그 제작비용이 크게 절감되고 유연한 물성으로 다양한 Device에 적용가능하기 때문에 최근 많은 연구가 진행 되고 있다. 현재 많은 연구팀에서 10% 이상의 효율을 가지는 단일 층의 Bulk-heterojunction(BHJ) 고분자 태양전지가 보고되고 있다. 이 논문에서는 fluorine이 도입된 Quinoxaline을 electron-withdrawing 물질로 이용하여 다양한 공액고분자를 합성하였고 그 특성을 분석 하였다. Florine이 하나 또는 두 개가 도입되었을 때, π- conjugation system이 확장 되었을 때, regioregular한 배열을 가졌을 때, sidechain의 배열이 바뀌었을 때, 각각 고분자태양전지의 효율에 어떠한 영향을 미치는지에 대해 연구를 실시하였다. 그 결과 10개의 고분자는 1.29 ~ 5.95% 의 광 전환 효율을 얻었고, 그 중 YJ-53가 0.74의 Voc 11.76의 Jsc 0.68의FF 와 5.95%의 광 전환 효율을 보였다.
Author(s)
KeumSangHa
Issued Date
2016
Awarded Date
2016. 8
Type
Dissertation
Keyword
OPVs Polymer Solar Cells 공액고분자 플로로기 퀴녹살린
Publisher
부경대학교 대학원
URI
https://repository.pknu.ac.kr:8443/handle/2021.oak/13274
http://pknu.dcollection.net/jsp/common/DcLoOrgPer.jsp?sItemId=000002299595
Alternative Author(s)
금상하
Affiliation
부경대학교 대학원
Department
대학원 공업화학과
Advisor
진영읍
Table Of Contents
Chapter I. Introduction 1
I-1. The Background of Polymer Solar Cells (PSCs) 1
I-2. Operating Mechanism of PSCs 2
I-3. Bulk Heterojunction Structure 3
I-4. Parameters of PSCs 5
I-4-1. Open-Circuit Voltage (Voc) 5
I-4-2. Short-Circuit Current Density (Jsc) 6
I-4-3. Fill Factor (FF) 6
I-5. Tactics to Synthesize Conjugated Polymers for High Performance 7
I-5-1. Regioregular Conjugated Polymers 7
I-5-2. Effects of Substitution Introduced in Conjugated Backbone 9
I-5-3.Donor-Acceptor (D-A) Alternating Structure 10
I-5-4.Selection of Donor and Acceptor Unit in Conjugated Polymer 12
Chapter II. Experimental 13
II-1. Materials and Instruments 13
II-2. Synthesis of monomers 15
II-2-1. Synthesis of donor monomers 15
II-2-1-1. Synthesis of thiophene-3-carbonyl chloride 15
II-2-1-2. Synthesis of N,N-diethylthiophene-3-carboxamide 15
II-2-1-3. Synthesis of benzo[1,2-b:4,5-b']dithiophene-4,8-dione 16
II-2-1-4. Synthesis of 4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene 17
II-2-1-5. Synthesis of 2,6-bis(trimethyltin)-4,8-bis(2-ethylhexyloxy)benzo[1,2-b:3,4-b′]dithiophene 17
II-2-2. Synthesis of acceptor monomers 20
II-2-2-1. Synthesis of 2,3-difluoro-1,4-bis-(trimethylsilyl)benzene 20
II-2-2-2. Synthesis of 1,4-dibromo2,3-difluoro-benzene 20
II-2-2-3. Synthesis of 1,4-dibromo-2,3-difiuoro-5,6-dinitro-benzene 21
II-2-2-4. Synthesis of 3,6-dibromo-4,5-difluorobenzene-1,2-diamine 21
II-2-2-5. Synthesis of hexacosane-13,14-dione 22
II-2-2-6. Synthesis of 5,8-dibromo-6,7-difluoro-2,3-didodecylquinoxaline 23
II-2-2-7. Synthesis of 2,5-dibromo-4-fluoro-nitrobenzene 25
II-2-2-8. Synthesis of Synthesis of N-(2’,5’-dibromo-4’-fluorophenyl)-2,2,2-trifluoroacetamide 25
II-2-2-9. Synthesis of N-(2’,5’-dibromo-4’-fluoro-6’-nitrophenyl)-2,2,2-trifluoroacetamide 26
II-2-2-10. Synthesis of 2,5-dibromo-4-fluoro-6-nitroaniline 26
II-2-2-11. Synthesis of 2,5-dibromo-4-fluoro-5,6-benzenediamine 27
II-2-2-12. Synthesis of 5,8-dibromo-2,3-didodecyl-6-fluoroquinoxaline 27
II-2-2-13. Synthesis of tributyl(thiophen-2-yl)stannane 30
II-2-2-14. Synthesis of 2,3-didodecyl-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline 30
II-2-2-15. Synthesis of 5,8-bis(5-bromothiophen-2-yl)-2,3-didodecyl-6,7-difluoroquinoxaline 31
II-2-2-16. Synthesis of 2,3-didodecyl-6-fluoro-5,8-di(thiophen-2-yl)quinoxaline 31
II-2-2-17. Synthesis of 5,8-bis(5-bromothiophen-2-yl)-2,3-didodecyl-6-fluoroquinoxaline 32
II-2-2-18. Synthesis of tributyl(3-hexylthiophen-2-yl)stannane 34
II-2-2-19. Synthesis of 2,3-didodecyl-6,7-difluoro-5,8-bis(3'-hexyl-[2,2'-
bithiophen]-5-yl)quinoxaline 34
II-2-2-20. Synthesis of 5,8-bis(5'-bromo-3'-hexyl-[2,2'-bithiophen]-5-yl)-2,3-
didodecyl-6,7-difluoroquinoxaline 35
II-2-2-21. Synthesis of tributyl(4-hexylthiophen-2-yl)stannane 36
II-2-2-22. Synthesis of 2,3-didodecyl-6,7-difluoro-5,8-bis(4'-hexyl-[2,2'-bithiophen]-5-yl)quinoxaline 37
II-3. Synthesis of polymers 40
II-3-1. Synthesis of poly[8-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)-2,3-didodecyl-6-fluoro-5-phenylquinoxaline] (YJ-51) 40
II-3-2. Synthesis of poly[5-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)-2,3-didodecyl-6,7-difluoro-8-phenylquinoxaline] (YJ-52) 42
II-3-3. Synthesis of poly[8-(5-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-2,3-didodecyl-6-fluoro-5-(5-phenylthiophen-2-yl)quinoxaline] (YJ-53) 44
II-3-4. Synthesis of poly[5-(5-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-2,3-didodecyl-6,7-difluoro-8-(5-phenylthiophen-2-yl)quinoxaline] (YJ-54) 46
II-3-5. Synthesis of poly[8-(5-(4,8-bis((2-ethylhexyl)oxy)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-2,3-didodecyl-6-fluoro-5-(5-phenylthiophen-2-yl)quinoxaline] (YJ-55) 48
II-3-6. Synthesis of poly[8-(5-(4,8-bis((2-ethylhexyl)oxy)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-2,3-didodecyl-6-fluoro-5-(5-phenylthiophen-2-yl)quinoxaline] (YJ-56) 48
II-3-7. Synthesis of poly[5-(5'-(4,8-bis((2-ethylhexyl)oxy)-6-methylbenzo[1,2-b:4,5-b']dithiophen-2-yl)-3'-hexyl-[2,2'-bithiophen]-5-yl)-2,3-didodecyl-6,7-difluoro-8-(3'-hexyl-5'-methyl-[2,2'-bithiophen]-5-yl)quinoxaline] (YJ-57) 50
II-3-8. Synthesis of poly[5-(5'-(4,8-bis((2-ethylhexyl)oxy)-6-methylbenzo[1,2-b:4,5-b']dithiophen-2-yl)-4'-hexyl-[2,2'-bithiophen]-5-yl)-2,3-didodecyl-6,7-difluoro-8-(4'-hexyl-5'-methyl-[2,2'-bithiophen]-5-yl)quinoxaline] (YJ-58) 52
II-3-9. Synthesis of poly[2,5-bis(2-butyloctyl)-3-(5-(2,3-didodecyl-6,7-difluoro-8-phenylquinoxalin-5-yl)thiophen-2-yl)-6-(5-phenylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] (YJ-59) 53
II-3-10. Synthesis of poly[2,5-bis(2-butyloctyl)-3-(5'-(2,3-didodecyl-6,7-difluoro-8-(5-phenylthiophen-2-yl)quinoxalin-5-yl)-[2,2'-bithiophen]-5-yl)-6-(5-phenylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] (YJ-60) 55
Chapter III. Results and Discussion 57
III-1. Polymerization results 57
III-2. Optical Properties of Polymers 59
III-3. Electrochemical Properties of Polymers 66
III-4. Photovoltaic Properties of Polymers 70
Chapter IV. Conclusions 74
References 75
Degree
Master
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