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Synthesis, Characterization and Photovoltaic Properties of Novel Alternating Copolymers Including Quinoxaline with Fluoro Group

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Abstract: 본 논문은 유기 발광소자와 고분자 태양전지의 효율을 향상시키기 위한 활성층 내 새로운 공액 고분자 개발을 연구한 결과이다. 고갈되어가는 화석연료를 대처할 수 있는 많은 대체에너지 자원 중에서 유기물을 이용하는 유기태양전지는 다른 태양전지들에 비해 경제성과 제작용이성에서 뛰어나 가장 유망한 차세대 태양전지로 고려되어 최근 국내외에서 많은 연구가 이루어지고 있다. 낮은 밴드갭을 가지는 전도성 고분자를 이용한 유기태양전지는 흡광 계수가 높아 얇은 박막으로도 태양빛을 충분히 흡수할 수 있어 얇은 소자 제작이 가능, 가벼우며, 구부릴 수 있으며, 대면적의 박막으로 만들 수 있는 장점으로 특히 신재생에너지 소재로 주목 받고 있다.
Polymer solar cells의 가장 대표적인 기법Bulk Heterojucntion D-A system에서 acceptor로 사용 되는 5,8-Dibromo-6,7-difluoro-2,3-dihexylquinoxaline 유도체는 높은 전공 이동성과 낮은 HOMO 에너지 값을 가지게 함으로써 작은 band gap을 밴드갭을 나타낸다. Donor물질은 bis(trimethyltin)-4,8-bis(2-octyloxy)benzo[1,2-b:3,4-b']dithiophene, 4,4-bis(2-ethylhexyl)-4H-cyclopenta[1,2-b:5,4-b']dithiophene, 4,4-dioctyl-4H-silolo[3,2-b:4,5-b']dithiophene, 2,7-dibromo-9,9-bis(2-ethylhexyl)-9H-fluorene, 2,7-dibromo-9-(heptadecan-9-yl)-9H-carbazole 를 사용하여 Stille, Suzuki 중합으로 고분자를 합성하였다. 이를 분자량, 열적 안정성, UV-vis 흡수 등을 측정을 통하여 고분자의 특성을 살펴보았다.

Author(s): 최효일

Issued Date: 2013

Awarded Date: 2013. 8

Type: Dissertation

Publisher: 부경대학교

URI: https://repository.pknu.ac.kr:8443/handle/2021.oak/25422
http://pknu.dcollection.net/jsp/common/DcLoOrgPer.jsp?sItemId=000001966495

Alternative Author(s): Choi, Hyo IL

Affiliation: 대학원

Department: 대학원 공업화학과

Advisor: 진영읍

Table Of Contents: Contents ……………………………………………………………………… I
Abstract ………………………………………………………………………VI

Chapter I. Introduction…………………………………………………………1

I-1. The Background of Organic Photovoltaics (OPVs) …………………1

I-2. Organic photovoltaic materials and devices……………………………… 6

I-3. Progress in design, synthesis, and control of materials……………… 14
I-3-1. Low-bandgap polymer design ………………………………………14
I-3-2. Push–pull conjugated polymers ……………………………………… 16
I-3-3. Single-layer devices …………………………………………………… 18
I-3-4. Tandem devices ………………………………………………………20

Chapter II. Results and Discussion ………………………………………………24

II-1. Synthesis and Characterization ..………………………………………… 24
II-1-1. Preparation of monomer ...………………………………………………24
II-1-1-1. Preparation of 5,8-Dibromo-6,7-difluoro-2,3-dihexylquinoxaline.24
II-1-1-2. Preparation of 5,8-bis(5-bromothiophen-2-yl)-6,7-difluoro-2,3-dihexylquinoxaline………………………………………………26
II-1-1-3. Preparation of 4,4-bis(2-ethylhexyl)-4H-cyclopenta[1,2-b:5,4-b']
Dithiophene……………………………………………………...27
II-1-1-4. Preparation of 2,6-bis(trimethyltin)-4,8-bis(2-octyloxy)benzo[1,2-b:3,4-b′]dithiophene………………………………………………28
II-1-1-5. Preparation of 4,4-dioctyl-2,6-bis(trimethylstannyl)-4H-silolo[3,2-b:4,5-b']dithiophene………………………………………………30
II-1-1-6. Preparation of 2,2'-(9,9-bis(2-ethylhexyl)-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)………………31
II-1-1-7. Preparation of 9-(heptadecan-9-yl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole……………………………33
II-1-2. Preparation of polymer…………………………………………………35
II-1-2-1. Preparation of 5-(4,8-bis(octyloxy)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-phenylquinoxaline (YJ-6)……………………………………………………………35
II-1-2-2. Preparation of 5-(4,4-bis(2-ethylhexyl)-6-methyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-methylquinoxaline(YJ-7)………………………………………36
II-1-2-3. Preparation of 6,7-difluoro-2,3-dihexyl-5-methyl-8-(6-methyl-4,4-dioctyl-4H-silolo[3,2-b:4,5-b']dithiophen-2-yl)quinoxaline
(YJ-8)……………………………………………………………37
II-1-2-4. Preparation of 5-(5-(4,8-bis(octyloxy)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-(5-phenylthiophen-2-yl)quinoxaline
(YJ-9)……………………………………………………………38
II-1-2-5. Preparation of 5-(5-(9,9-bis(2-ethylhexyl)-7-phenyl-9H-fluoren-2-yl)thiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-(5-phenylthiophen-2-yl)quinoxaline (YJ-10)……………………………………………39
II-1-2-6. Preparation of 2-(5-(6,7-difluoro-2,3-dihexyl-8-(5-phenylthiophen-2-yl)quinoxalin-5-yl)thiophen-2-yl)-9-(heptadecan-9-yl)-7-phenyl-9H-carbazole (YJ-11)……………………………………………40

II-2. Characterization of the Polymers ………………………………………… 41
II-3. Optical Properties of the Polymer………………………………………… 43
II-4. Electrochemical Properties of the Polymer………………………………… 46
II-5. Photovoltaic Properties of the Polymer…………………………………… 49

Chapter III. Conclusions……………………………………………………… 53

Chapter IV. Experimental………………………………………………………54

IV-1. Synthesis of acceptor monomer…………………………………………56
IV-1-1. Synthesis of 2,3-Difluoro-1,4-bis-(trimethylsilyl)benzene (2)……56
IV-1-2. Synthesis of 1,4-dibromo2,3-Difluoro-benzene (3)………………56
IV-1-3. Synthesis of 1,4-dibromo-2,3-difiuoro-5,6-dinitro-benzene (4)……57
IV-1-4. Synthesis of 3,6-dibromo-4,5-difluorobenzene-1,2-diamine (5)……57
IV-1-5. Synthesis of Tetradecane-7,8-dione (6)……………………………58
IV-1-6. Synthesis of 5,8-Dibromo-6,7-difluoro-2,3-dihexylquinoxaline (9)23

IV-2. Synthesis of acceptor monomer…………………………………………59
IV-2-1. Synthesis of 6,7-difluoro-2,3-dihexyl-5,8-di(thiophen-2-yl) quinoxaline (12)………………………………………………………60
IV-2-2. Synthesis of 5,8-bis(5-bromothiophen-2-yl)-6,7-difluoro-2,3-dihexylquinoxaline (13)………………………………………………30

IV-3. Synthesis of donor monomer……………………………………………61
IV-3-1. Synthesis of Di-3-thienylmethanol (16)……………………………61
IV-3-2. Synthesis of Di-3-thienylmethane (17)……………………………61
IV-3-3. Synthesis of Bis(2-bromothien-3-yl)methane (18)…………………62
IV-3-4. Synthesis of 4H-Cyclopenta[2,1-b:3,4-b(]dithiophene (19)………63
IV-3-5. Synthesis of 4,4-Di(2-ethtylhexyl)-4H-cyclopenta[2,1-b:3,4-b(]dithiophene (20)…………………………………………………63

IV-4. Synthesis of donor monomer……………………………………………64
IV-4-1. Synthesis of thiophene-3-carbonyl chloride (22)……………………64
IV-4-2. Synthesis of N,N-diethylthiophene-3-carboxamide (23)……………64
IV-4-3. Synthesis of 4,8-dihydrobenzo[1,2-b:4,5-b′]dithiophen-4,8
-dione (24) …………………………………………………………65
IV-4-4. Synthesis of 4,8-Bis(2-octyloxy)benzo[1,2-b:3,4-b]
dithiophene (25)…………………………………………………66
IV-4-5. Synthesis of ,6-Bis(trimethyltin)-4,8-bis(2-octyldodecyloxy)
benzo[1,2-b:3,4-b′]dithiophene (26)…………………………………67

IV-5. Synthesis of donor monomer……………………………………………68
IV-5-1. Synthesis of 3,3’-Dibromo-2,2’-bithiophene (28)…………………68
IV-5-2. Synthesis of 3,3’-Di-n-octylsilylene-2,2’-bithiophene (29)…………68
IV-5-3. Synthesis of 5,5’Bis(trimethylstannyl)-3,3’-Di-n-dodecylsilylene-2,2’-bithiophene (30)………………………………………………69

IV-6. Synthesis of donor monomer……………………………………………70
IV-6-1. Synthesis of 2,7-dibromofluorene (32)……………………………70
IV-6-2. Synthesis of 2,7-Dibromo-9,9'-bis(2-ethylhexyl)fluorene (33)……71
IV-6-3. Synthesis of 2,2'-(9,9-Bis(n-propyl)-fluoren-2,7-diyl)-bis[4,4,5,5-tetramethyl-[1,3,2]dioxaborolane] (34)……………………………72

IV-7. Synthesis of donor monomer……………………………………………73
IV-7-1. Synthesis of 4,4'-Dibromo-2-nitrobiphenyl (36)……………………73
IV-7-2. Synthesis of 2,7-Dibromocarbazole (37)……………………………74
IV-7-3. Synthesis of octylmagnesium bromide (39)…………………………74
IV-7-4. Synthesis of Heptadecan-9-ol (40)…………………………………75
IV-7-5. Synthesis of 9-Heptadecane p-toluenesulfonate (41)………………76
IV-7-6. Synthesis of 2,7-Dibromo-9-(heptadec-9-yl)carbazole (42)…………76
IV-7-7. Synthesis of 2,7-Bis(4’,4’,5’,5’-tetramethyl-1’,3’,2’-dioxaborolan-2’-yl)-N-9”-heptadecanylcarbazole (43)……………………………77

IV-8. Synthesis of polymer……………………………………………………78
IV-8-1. Synthesis of Poly-(5-(4,8-bis(octyloxy)-6-phenylbenzo[1,2-b:4,5-b']dithiophen-2-yl))-6,7-difluoro-2,3-dihexyl-8-phenylquinoxaline (YJ-6)………………………………………………………………78
IV-8-2. Synthesis of 5-(4,4-bis(2-ethylhexyl)-6-methyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-methylquinoxaline(YJ-7)……………………………………………79
IV-8-3. Synthesis of 6,7-difluoro-2,3-dihexyl-5-methyl-8-(6-methyl-4,4-dioctyl-4H-silolo[3,2-b:4,5-b']dithiophen-2-yl)quinoxaline (YJ-8)…79
IV-8-4. Synthesis of 5-(5-(4,8-bis(octyloxy)-6-phenylbenzo[1,2-b:4,5-]
dithiophen-2-yl)thiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-(5-phenylthiophen-2-yl)quinoxaline (YJ-9)……………………………80
IV-8-5. Synthesis of 5-(5-(9,9-bis(2-ethylhexyl)-7-phenyl-9H-fluoren-2-yl)thiophen-2-yl)-6,7-difluoro-2,3-dihexyl-8-(5-phenylthiophen-2-yl)quinoxaline (YJ-10)……………………………………………81
IV-8-6. Synthesis of 2-(5-(6,7-difluoro-2,3-dihexyl-8-(5-phenylthiophen-2-yl)quinoxalin-5-yl)thiophen-2-yl)-9-(heptadecan-9-yl)-7-phenyl-9H-carbazole (YJ-11)……………………………………………………81

References………………………………………………………………………83

Degree: Master

Appears in Collections:: 대학원 > 공업화학과

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