유기 광전자 소자에 사용되는 층간 소재의 합성 및 적용
- Alternative Title
- Interface Materials and Their Applications of the Organic Opto-Electronic Devices
- Abstract
- 본 연구는 소자의 성능을 향상 시키기 위한 정공 및 전자 주입/전달 소재의 합성 및 합성한 소재들의 적용에 대한 연구논문이다. Triphenlyamine (TPA)는 뛰어난 전자 제공물질로 알려져 있으며, 정공 주입/전달 층으로 많이 연구 된다. 또한 열경화가 가능한 물질은 열경화시 뛰어난 용제 저항성과 전기 화학적 안정성을 가지고 있기 때문에 정공 주입/전달 물질로 적합하다. 용재 저항성을 부여하기 위해 TPA에 열경화가 가능한 vinyl기를 포함시킨 oligomer형태의 물질을 합성했다. 열적 거동을 알아보기 위하여 시차 주사 열량측정법 (differential scanning calorimetry, DSC)으로 분석하였으며, 열경화 온도를 180 oC로 정하였다. UV-Vis spectroscopy 및 순환 전압 전류법 (cyclic voltammetry, CV) 를 이용하여 우수한 내용매성을 가지는 것을 확인하였으며, 호모( highest occupied molecular orbital (HOMO)) 에너지 준위가 -5.09 eV이며 정공 주입소재로 적합함을 확인했다. 합성한 TPA oligomer를 유기 발광 소자의 정공 수송/주입층으로 사용하였을 때, 사용하지 않은 소자보다 발광효율 및 소자의 성능이 향상됨을 확인했다.
또한 알킬기 말단에 quaternary ammonium salt를 가진 water/alcohol soluble π-conjugated polymer를 전자 주입/전달 층으로 사용하면 금속 음전극의 일함수가 작아져 유기 광전자 소자의 효율을 향상시킨 다는 연구결과가 있다. 하지만 polymer는 합성의 재현성 및 제조 공정이 복잡하다는 단점이 있다. 따라서 polymer보다 합성 재현성이 높고 제조공정이 쉬운 oligomer형태의 water/alcohol soluble π-conjugated 물질을 합성했다. 합성한 oligomer는 물 또는 알코올에 잘 용해 되며, 유기용매에 대한 내용매성을 가진다. 자외선 광전자 분광법 (ultraviolet photoelectron spectroscopy, UPS)으로 water/alcohol soluble π-conjugated oligomer가 금속전극의 일함수를 감소 시키는 것을 확인했다.
물과 알코올에 잘 용해되는polyvionogen을 유기 태양전지 소자의 전자 주입/전달 층으로 적용했다. Polyviologen의 counter anion (CA) (bromide (Br-), tosylate (OTs-), tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), tetraphenlyborate (BPh4-))의 종류에 따른 유기 태양전지 소자의 성능변화를 확인하였다. Polyviologen 유도체들을 X선 광전자 분광법(X-ray Photoelectron Spectroscopy, XPS)으로 분석한 결과CA의 교환을 확인 하였다. UPS으로 금속전극(Al)의 일함수의 감소를 확인했다. Polyviologen의 CA에 따라 소자의 성능이 변화되는 것을 확인했다. BPh4-를 가진 polyviologen이 전자 수송/전달 층으로 사용된 유기 태양전지 소자의 contact property가 가장 좋은 것을 확인했고, photo conversion efficiency (PCE)가 가장 좋은 것을 확인했다.
- Issued Date
- 2014
- Awarded Date
- 2014. 2
- Type
- Dissertation
- Publisher
- 부경대학교
- Alternative Author(s)
- HeeSeob Hong
- Affiliation
- 대학원
- Department
- 대학원 고분자공학과
- Advisor
- 김주현
- Table Of Contents
- Contents I
List of Figures IX
List of Tables XI
List of Schemes XII
Abstract XIII
Chapter I. Introduction 1
I-1. Introduction of the opto-electronic device with organic materials 1
I-2. The architectures and the operating principle of organic opto-electronic device 3
I-2-1. The operating principle of an organic light emitting diode (OLED) 3
I-2-2. The operating principle of an organic solar cell (OSC) 4
I-3. Electrode buffer layer 5
I-3-1. Anode buffer layer (ABL) 6
I-3-1-1. Poly(3,4-ethylenedioxithiophene):poly(styrene sulfonic acid) 6
I-3-1-2. Cross-linkable materials 7
I-3-2. Cathode buffer layer (CBL) 7
I-3-2-1. Lithium fluoride (LiF) 8
I-3-2-2. Water/alcohol soluble material 8
I-3-2-3. Polyviologen 9
Chapter II. Synthesis and characterization of thermally cross-linkable trimer based on triphenylamine 10
II-1. Introduction 10
II-2. Experimental 11
II-2-1. Materials and synthesis 11
II-2-1-1. Materials 11
II-2-1-2. Synthesis 11
II-2-1-2-1. Synthesis of (4-butyl-phenyl)-diphenyl-amine (1) 11
II-2-1-2-2. Synthesis of bis-(4-bromo-phenyl)-(4-butyl-phenyl)-amine (2) 12
II-2-1-2-3. Synthesis of (4-butyl-phenyl)-bis-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxa-borolan-2-yl)-phenyl]-amine (3) 13
II-2-1-2-4. Synthesis of 4-[(4-bromo-phenyl)-(4-butyl-phenyl)-amino]-benz-aldehyde (4) 14
II-2-1-2-5. Synthesis of (4-Butyl-phenyl)-bis-[4-((4-formyl-phenyl)-(4-butyl-phenyl)-phenyl-amine)-phenyl]-amine (5) 16
II-2-1-2-6. Synthesis of (4-butyl-phenyl)-bis-[4-((4-vinyl-phenyl)-(4-butyl-phenyl)-phenyl-amine)-phenyl]-amine (3-TPA) 17
II-2-2. Device fabrication 20
II-2-3. Measurements 20
II-3. Results and discussion 21
II-3-1. Thermal analysis of 3-TPA 21
II-3-2. Optical properties of 3-TPA 24
II-3-3. Electrochemical properties of 3-TPA 26
II-3-4. OLEDs properties of 3-TPA 28
II-4. Conclusions 31
Chapter III. π-Conjugated oligomers as cathode buffer Layer 32
III-1. Introduction 32
III-2. Experimental 32
III-2-1. Materials and synthesis 32
III-2-1-1. Materials 33
III-2-1-2. Synthesis 33
III-2-1-2-1. Synthesis of (6-bromo-hexyl)-9H-carbazole (1) 33
III-2-1-2-2. Synthesis of 3,6-dibromo-9-(6-bromo-hexyl)-9H-carbazole (2) 34
III-2-1-2-3. Synthesis of 9-(6-bromo-hexyl)-3,6-bis-(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolan-2-yl)-9H-carbazole (3) 35
III-2-1-2-4. Synthesis of 3,6-dibromo-9-hexyl-9H-carbazole (4) 36
III-2-1-2-5. Synthesis of 9-hexyl-3,6-bis-(4,4,5,5-tetramethyl-[1,3,2]di-oxaborolan-2-yl)-9H-carbazole (5) 37
III-2-1-2-6. Synthesis of 10-hexyl-3,7-bis-(4,4,5,5-tetramethyl-[1,3,2]di-oxaborolan-2-yl)-10H-phenothiazine (6) 38
III-2-1-2-7. Synthesis of 10-(4-bromo-butyl)-10H-phenothiazine (7) 39
III-2-1-2-8. Synthesis of 3,7-dibromo-10-(4-bromobutyl)-10H-pheno-thiazine (8) 40
III-2-1-2-9. Synthesis of 10-(4-bromo-butyl)-3,7-bis-(4,4,5,5-tetra-methyl-[1,3,2]-dioxaborolan-2-yl)-10H-phenothiazine (9) 41
III-2-1-2-10. Synthesis of 2-bromo-9,9-bis(6-bromohexyl)-9H-fluorene (10) 42
III-2-1-2-11. Synthesis of 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (11) 43
III-2-1-2-12. Synthesis of 2-(9,9-bis(6-bromohexyl)-2-(4,4,5,5-tetra-methyl-1,3,2-dioxaborol-an-2-yl)-9H-fluoren-7-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12) 44
III-2-1-2-13. General procedure of the suzuki coupling reaction 46
III-2-1-2-13-1. Synthesis of 3,7-bis[9,9-bis(6-bromohexyl)-9H-fluoren-2-yl]-10-(4-bromo-butyl)-10H-phenothiazine (13) 46
III-2-1-2-13-2. Synthesis of 3,6-bis-[9,9-bis-(6-bromo-hexyl)-9H-fluo-ren-2-yl]-9-(6-bromo-hexyl)-9H-carbazole (14) 47
III-2-1-2-13-3. Synthesis of 9,9,9',9',9'',9''-hexakis-(6-bromo-hexyl)-9H,-9'H,9''H-[2,3';6',2'']-terfluorene (15) 48
III-2-1-2-13-4. Synthesis of 3,7-bis-[9,9-bis-(6-bromo-hexyl)-9H-fluo-ren-2-yl]-10-hexyl-10H-phenothiazine (16) 49
III-2-1-2-13-5. Synthesis of 3,6-bis-[9,9-bis-(6-bromo-hexyl)-9H-fluo-ren-2-yl]-9-hexyl-9H-carbazole (17) 50
III-2-1-2-14. Synthesis of 3,7-bis[9,9-bis(6-(N,N,N-trimetylammonium)-hexyl)-9H-fluoren-2-yl]-10-(4-(N,N,N-trimetylammonium)-butyl)-10H-phenothiazine pentabromide (FPiF) 51
III-2-1-2-15. Synthesis of 3,6-bis-[9,9-bis-(6-(N,N,N-trimetyl-ammonium)-hexyl)-9H-fluoren-2-yl]-9-(6-(N,N,N-trimetyl-ammonium)-hexyl)-9H-carbazole (FCiF) 51
III-2-1-2-16. Synthesis of 9,9,9',9',9'',9''-bexakis-(6-(N,N,N-trimetylam-monium)-hexyl)-9H,9'H,9''H-[2,3';6',2'']terfluorene (FFiF) 52
III-2-1-2-17. Synthesis of 3,7-bis[9,9-bis(6-(N,N,N-trimetylammonium)-hexyl)-9H-fluoren-2-yl]-10-hexyl-10H-phenothiazine penta-bromide (FPF) 52
III-2-1-2-18. Synthesis of 3,6-bis-[9,9-bis-(6-(N,N,N-trimetyl-ammonium)-hexyl)-9H-fluoren-2-yl]-9-hexyl-9H-carbazole (FCF) 53
III-2-2. Fabrication of devices 56
III-2-3. Measurements 57
III-3. Results and discussion 57
III-3-1. Ultraviolet photoelectron spectroscopy (UPS) 57
III-3-2. Photovoltaic properties 60
III-4. Conclusions 65
Chapter IV. Effect of counter anion of polyviologen on the photovoltaic properties 66
IV-1. Introduction 66
IV-2. Experimental 66
IV-2-1. Materials and synthesis 66
IV-2-1-1. Materials 66
IV-2-1-2. Synthesis 67
IV-2-1-2-1. Synthesis of poly (1,1'-didodecyl-4,4'-bipyridinium dibro-mide) (PV12-Br) 67
IV-2-1-2-2. General procedure of the anion exchange reaction 67
IV-2-1-2-2-1 Synthesis of poly (1,1'-didodecyl-4,4'-bipyridinium di-tetrafluoroborate) (PV12-BF4) 68
IV-2-1-2-2-2. Synthesis of poly (1,1'-didodecyl-4,4'-bipyridinium di-hexafluorophosphate) (PV12-PF6) 68
IV-2-1-2-2-3. Synthesis of poly (1,1'-didodecyl-4,4'-bipyridinium di -p-toluenesulfonate) (PV12-OTs) 69
IV-2-1-2-2-4 Synthesis of poly (1,1'-didodecyl-4,4'-bipyridinium di-tetraphenylborate) (PV12-BPh4) 69
IV-2-2. Fabrication of devices 72
IV-2-3. Measurements 72
IV-3. Results and discussion 72
IV-3-1. XPS elemental analysis 72
IV-3-2. UPS study 74
IV-3-3. OSCs properties of PV12 derivative 76
IV-4. Conclusions 80
V. Reference 81
- Degree
- Master
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