Design and Synthesis of Organic Small Molecules for Application of Organic Electronics
- Alternative Title
- 유기전자제품의 응용을 위한 유기 분자 물질의 설계 및 합성
- Abstract
- For the past few decades Organic electronics are increasing its command on world’s economy, because of its extraordinary wisdom in academic and commercialization of lightning, medical laboratories (biosensors), communication (mobile phones) and media (televisions, printed electronics) transformation and its essential use in human life. Among all organic electronic devices organic light emitting devices (OLEDs), organic photovoltaics (OPVs), and organic thin film transistors (OTFTs) or organic field effect transistor (OFETs) have been studied widely. OTFTs are increasing its interest towards development in organic semiconductors because of its unique usage in OLEDs, biosensors and printed electronic, etc. Here, we designed and synthesized many efficient organic small molecules with the core structures of benzothiadiazole (BTD), [1]benzothieno[3,2-b]benzo-thiophene (BTBT), and quinoxaline (QXN) derivatives. The BTD-based molecules exhibited p-channel characteristics with a maximum hole mobility of 0.10 cm2 V-1 s-1 with current on/off ratio > 107 for top-contact/bottom-gate OTFT devices. Interestingly, the OTFT devices fabricated using a blend of BTD-based molecule (p-type semiconductor) and PDIFCN2 (n-type semiconductor) displayed ambipolar transistor characteristics with balanced hole and electron mobility of 0.10 and 0.07 cm2 V-1 s-1, respectively. Furthermore, a complementary-like inverter using ambipolar TFT were fabricated using BTD-based molecules showed high voltage gain of 84. On the other hand, the newly synthesized BTBT derivatives showed a remarkable maximum hole mobility of 0.58 cm2V-1S-1 with 106-109 on/off ratios. Whereas, the QXN-based molecules generally displayed poor hole mobilities (1.7 ×10-4 cm2 V-1 s-1). However, we noted that tuning the molecular structure of QXN based molecule might be very much useful for OLEDs. Therefore, we synthesized new QXN-based donor-acceptor-donor (D-A-D) molecule (DCQ-1) containing carbazole (CBZ) as donor and QXN as an acceptor, and the resulting molecule found to be a yellow light emitter. The OLEDs made with QXN-based molecule gave a maximum EQE of 24.6% at 3000 cd/m2.
- Issued Date
- 2019
- Awarded Date
- 2019. 2
- Type
- Dissertation
- Publisher
- 부경대학교
- Affiliation
- 부경대학교 대학원
- Department
- 대학원 화학과
- Advisor
- 서성용
- Table Of Contents
- Contents
Abstract xxi
Abstract (Korean) xxiii
Chapter 1. Introduction 1
1.1. Organic thin film transistors 2
1.1.1. OTFT definition 4
1.1.2. OTFT structure 5
1.1.3. Working principle of OTFT 8
1.1.4. OTFT materials 9
1.1.5. Encapsulation methods 12
1.1.6. N-type and P-type 15
1.1.7. Characteristic parameters 16
1.2. Organic light emitting diodes 20
Chapter 2. Synthesis and characterization of benzothiadiazole derivatives for OTFT 29
2.1. Introduction 32
2. 2. Experimental 33
2.2.1. General Methods 33
2.2.2. Synthesis 33
2.2.2.1. Synthesis of ((4-bromophenyl)ethynyl)trimethylsilane (1) 33
2.2.2.2. Synthesis of trimethyl((4-(thiophen-2-yl)phenyl)ethynyl)silane 34
2.2.2.3. Synthesis of 2-(4-ethynylphenyl)thiophene(3) 34
2.2.2.4. Synthesis of benzo[c][1,2,5]thiadiazole (4) 35
2.2.2.5. Synthesis of 4,7-dibromobenzo[c][1,2,5]thiadiazole (5) 35
2.2.2.6. Synthesis of 4,7-diiodobenzo[c][1,2,5]thiadiazole(6) 36
2.2.2.7. Synthesis of 2-(4-bromophenyl)thiophene (7) 37
2.2.2.8. Synthesis of 4,4,5,5-tetramethyl-2-(4-(thiophen-2-yl)phenyl)- 1,3,2-dioxaborolane (8) 37
2.2.2.9. Synthesis of 2-phenylthiophene (9) 38
2.2.2.10. Synthesis of 5-phenylthiophen-2-yl-2-boronic acid (10) 38
2.2.2.11. Synthesis of 1-ethynyl-4-(trifluoromethyl)benzene 39
2.2.2.12. Synthesis of 4,7-bis((4-(thiophen-2-yl)phenyl)ethynyl)benzo[c]-[1,-2,5]thiadiazole (BTD-1) 39
2.2.2.13. Synthesis of 4,7-bis(5-phenylthiophen-2-yl)benzo[c][1,2,5]-thiadiazole (BTD-2) 40
2.2.2.14. Synthesis of 4,7-bis(4-(thiophen-2-yl)phenyl)benzo[c[1,2,5]thia-diazole (BTD-3) 41
2.2.2.15. Synthesis of 4,7-bis(2-(4-(trifluoromethyl)phenyl)ethynyl)-benzo[c][1,2,5]thiadiazole (BTD-4) 41
2.2.3. Theoretical calculation 42
2.2.4. Device fabrication 42
2.2.5. Characterization 42
2. 3. Results and discussion 45
2.3.1. Synthesis 45
2.3.2. Thermal, optical, and electrochemical properties 48
2.3.3. Theoretical calculation 51
2.3.4. Thin-film transistor characterization 55
2.3.5. Thin-film transistor and complementary inverter characterization 60
2.3.6. Thin-film microstructure and morphology 62
Chapter 3. Synthesis and Characterization of benzo[b]benzo[4,5]thieno[2,3-d]thiophene Derivative as Organic Semiconductors for Organic Thin-Film Transistors 60
3. 1. Introduction 68
3.2. Experimental 70
3.2.1. General Methods 70
3.2.2. Synthesis 70
3.2.2.1. Synthesis of 2-iodo[1]benzothieno[3,2-b]benzothiophene (BTBT-I) 70
3.2.2.2. Synthesis of 2-bromo-7-octyl-[1]benzothieno[3,2-b][1]benzothio-phene (R-BTBT-Br) 71
3.2.2.3. Synthesis of 2,7-diiodobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (DIBTBT) 71
3.2.2.4. Synthesis of 1-ethynyl-4-(trifluoromethyl)benzene 71
3.2.2.5. Synthesis of 2-thiopene[1]benzothieno[3,2-b]benzothiophene (BTBT-1) 72
3.2.2.6. Synthesis of 2-thiophene-7-octyl-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT-2 72
3.2.2.7. Synthesis of 2-(phenylethynyl)benzo[b]benzo[4,5]thieno[2,3-d]-thiophene (BTBT-3) 73
3.2.2.8. Synthesis of 2,7-bis(phenylethynyl)benzo[b]benzo[4,5]thieno-[2,3-d]thiophene (BTBT-4) 73
3.2.2.9. Synthesis of 2,7-bis((4-(trifluoromethyl)phenyl)ethynyl)benz[b]-benzo[4,5]thieno[2,3-d]thiophene (BTBT-5) 74
3.2.3. Theoretical calculation 75
3.2.4. Device fabrication 75
3.2.5. Characterization 76
3. 3. Results and discussion 76
3.3.1. Synthesis 77
3.3.2. Thermal, optical, and electrochemical properties 77
3.3.1. Comparison of the optical absorption spectra in solution and thin films 79
3.3.2. Theoretical calculation 85
3.3.3. Thin-film transistor characterization 87
3.3.4. Thin-film microstructure and morphology 92
Chapter 4. Synthesis and Characterization of Quinoxaline Derivative as Organic Semiconductors for Organic Thin-Film Transistors 99
4.1. Introduction 101
4.2. Experiment details 101
4.2.2. Synthesis 101
4.2.2.1. Synthesis of 5,8-dibromoquinoxaline (DBQ) 101
4.2.2.2. Synthesis of 5,8-dibromo-2,3-diphenylquinoxaline (DBDPQ) 102
4.2.2.3. synthesis of 5,8-dibromo-2,3-bis(4-methoxyphenyl)quinoxaline (DBDMOPQ) 103
4.2.2.4. Synthesis of 5,8-dibromo-2,3-di(thiophen-2-yl)quinoxaline (DBDTQ) 104
4.2.2.5. Synthesis of 1,2-bis(4-(thiophen-2-yl)phenyl)ethane-1,2-dione (11) 104
4.2.2.6. Synthesis of 1,2-bis(4-(phenylethynyl)phenyl)ethane-1,2-dione (12) 105
4.2.2.7. Synthesis of 1,2-bis(4-((trimethylsilyl)ethynyl)phenyl)ethane-1,2-dione: (13) 106
4.2.2.8. Synthesis of 1,2-bis(4-ethynylphenyl)ethane-1,2-dione: (14)106
4.2.2.9. Synthesis of 1,2-bis(4-((4-(trifluoromethyl)phenyl)ethynyl)-phenyl)ethane-1,2-dione: (15) 107
4.2.2.10. Synthesis of [1,1':4',1''-terphenyl]-2',3'-diamine (16) 107
4.2.2.11. Synthesis of 3,6-bis(phenylethynyl)benzene-1,2-diamine (17) 108
4.2.2.12. Synthesis of 3,6-di(thiophen-2-yl)benzene-1,2-diamine (18) 108
4.2.2.13. Synthesis of 5,8-bis(4-(thiophen-2-yl)phenyl)quinoxaline (QXN-1) 109
4.2.2.14. Synthesis of 5,8-bis(5-phenylthiophen-2-yl)quinoxaline (QXN-2) 109
4.2.2.15. Synthesis of 2,3,5,8-tetra(thiophen-2-yl)quinoxaline (QXN-3) 110
4.2.2.16. Synthesis of 5,8-diphenyl-2,3-di(thiophen-2-yl)quinoxaline (QXN-4) 111
4.2.2.17. Synthesis of 2,3-diphenyl-5,8-di(thiophen-2-yl)quinoxaline (QXN-5) 111
4.2.2.18. Synthesis of 2,3,5,8-tetraphenylquinoxaline (QXN-6) 112
4.2.2.19. Synthesis of 2,3-bis(4-methoxyphenyl)-5,8-diphenylquinoxaline (QXN-7) 113
4.2.2.20. Synthesis of 2,3-bis(4-methoxyphenyl)-5,8-bis(phenylethynyl)-quinoxaline (QXN-8) 113
4.2.2.21. Synthesis of 2,3-diphenyl-5,8-bis((4-(trifluoromethyl)phenyl)-ethynyl)quinoxaline (QXN-9) 114
4.2.2.22. Synthesis of 5,8-diphenyl-2,3-bis(4-(thiophen-2-yl)phenyl)quin-oxaline (QXN-10) 115
4.2.2.23. Synthesis of 5,8-bis(phenylethynyl)-2,3-bis(4-(thiophen-2-yl)phenyl)quinoxaline (QXN-11) 115
4.2.2.24. Synthesis of 2,3-diphenyl-5,8-bis(5-phenylthiophen-2-yl)-quinoxaline (QXN-12) 116
4.2.2.25. Synthesis of 5,8-diphenyl-2,3-bis(4-(phenylethynyl)phenyl)-quinoxaline (QXN-13) 116
4.2.2.26. Synthesis of 5,8-diphenyl-2,3-bis(4-(phenylethynyl)phenyl)-quinoxaline (QXN-14) 117
4.2.2.27. Synthesis of 5,8-diphenyl-2,3-bis(4-(phenylethynyl)phenyl)-quinoxaline (QXN-15) 117
4.2.3. Theoretical calculation 118
4.2.4. Device fabrication 118
4.2.5. Characterization 118
4.3. Results and discussion 118
4.3.1. Synthesis 118
4.3.2. Theoretical calculation 122
4.3.3. Thermal, optical, and electrochemical properties 124
4.3.4. Thin-film transistor characterization 128
4.3.5. Thin-film microstructure and morphology 130
Chapter 5. Synthesis and characterization of quinoxaline derivative for high performance phosphorescent organic light-emitting diodes 133
5.1. Introduction 133
5.2. Experimental 134
5.2.1. General methods 134
5.2.2. Synthesis 134
5.2.2.1. Synthesis of 2,3-di(9H-carbazol-9-yl)quinoxaline (DCQ) 134
5.2.3. Device fabrication and characterization 135
5.3. Results and discussion 136
Chapter 6. Work in-Progress 147
6.1. General Methods and materials 147
6.1.1. Synthesis of precursors 148
6.1.2. 2-((9H-fluoren-9-ylidene)methyl)thiophene 155
32-Fluorenone derivatives 155
6.1.4. 2-(9H-fluoren-9-ylidene)malononitrile 156
6.1.5. indeno[1,2-b]fluorene-6,12-dione derivatives 158
6.2. Results and discussion 163
Chapter 7. Conclusion 168
References 170
List of Tables
Table 1.2.1. NTSC and EBU standards for CIE coordinate 25
Table 2.1. Physical and electrochemical properties of the BTD-1 to 4 55
Table 2.2. TFT device performance parameters based on thin films of BTD-1,2,3 and BTD-4 62
Table 3.1. Physical and electrochemical properties of the BTBT-1 to 5 86
Table 3.2. TFT device performance parameters based on thin films of BTBT-1 to BTBT-5 91
Table 4.1. Physical and electrochemical properties of the QXN-5,6 and 12 127
Table 4.2. TFT device performance parameters based on thin films of QXN-1 to QXN-15 128
Table 5.1. Photophysical properties and energy levels of DCQ 137
List of Figures
Figure. 1.1.1. Representative molecular structures of polymers and small molecules for organic electronics 2
Figure. 1.1.2. Organic thin film transistor basic structure 4
Figure. 1.1.3. Organic thin film transistor applications 5
Figure. 1.1.4. Organic thin film transistor structures 8
Figure. 1.1.5. Representative molecular structures of OTFT materials 10
Figure 1.2.1. Transition processes and a typical OLED device structure 21
Figure 1.2.2. Energy level diagram and its mechanism for OLED 22
Figure. 1.2.3. Color coordination diagram for OLED 24
Figure. 1.2.4. Schematic illustration of molecular design strategy 26
Figure. 2.1. Chemical structure of BTD-1 to 4 32
Figure. 2.2. DSC graph of compounds (a) BTD-2 and (b) BTD-3 49
Figure. 2.3. TGA graphs of compounds (a) BTD-2 and (b) BTD-3 50
Figure. 2.4. Optical spectra of BTD-1 50
Figure. 2.5. Optical spectra of BTD-2 and BTD-3 51
Figure. 2.6. Molecular orbital surfaces of HOMO and LUMO by DFT calculation of BTD-1 52
Figure. 2.7. Molecular orbital surfaces of HOMO and LUMO by DFT calculation of (a) BTD-2 and (b) BTD-3 53
Figure. 2.8. CV of BTD-2 and (b) BTD-3 55
Figure. 2.9. OTFT device based on thin films out-puts of BTD-1 56
Figure. 2.10. OTFT devices based thin films out-puts of BTD-BTD-4 58
Figure. 2.11. OTFT devices based thin films out-puts of BTD-2 58
Figure. 2.12. Ambipolar OTFT devices based thin films out-puts of BTD-2:PDIFCN2 60
Figure. 2.13. CMOS based BHJ ambipolar TFT out-puts pf BTD-2 61
Figure. 2.14. AFM image of BTD-1 63
Figure. 2.15. XRD scans of BTD-2 and BTD-3 65
Figure. 2.16. AFM and XRD image of BTD-2 66
Figure. 2.17. AFM image of BTD-3 67
Figure. 2.18. AFM image of BTD-2 67
Figure. 3.1. Chemical structure of BTBT-1 to 5 70
Figure. 3.2. DSC of BTBT-4 and BTBT-5 80
Figure. 3.3. TGA graphs of BTBT-4 and BTBT-5 80
Figure. 3.4. Optical spectra of BTBT-1 and BTBT-2 81
Figure. 3.5. Optical spectra of BTBT-4 and BTBT-5 81
Figure. 3.6. Molecular orbital surfaces of HOMO and LUMO by DFT of BTBT-1 and BTBT-2 82
Figure. 3.7. Molecular orbital surfaces of HOMO and LUMO by DFT of BTBT-4 and BTBT-5 83
Figure. 3.8. CV of BTBT-1 and BTBT-2 84
Figure. 3.9. CV of BTBT-4 and BTBT-5 85
Figure. 3.10. OFET device out-put based on BTBT-2 86
Figure. 3.11. OTFT devices out-put of BTBT-4 88
Figure. 3.12. OFET device out-put of BTBT-2 89
Figure. 3.13. XRD scans and AFM image of BTBT-1 90
Figure. 3.14. XRD scans and AFM images of BTBT-2 93
Figure. 3.15. XRD scans of BTBT-2 94
Figure. 3.16. XRD scans of BTBT-4 94
Figure. 3.17 XRD scans of BTBT-5 95
Figure. 3.18. AFM image of BTBT-4 95
Figure.4.1. Molecular structures of QXN-1 to QXN-15 101
Figure. 4.2. Molecular orbital surfaces of HOMO and LUMO by DFT of QXN-5, 6, and 12 124
Figure. 4.3. TGA and DSC graphs of QXN-5, 6 and 12 125
Figure. 4.4. Optical spectra of QXN-5, 6 and 12 126
Figure. 4.5. CV of BTD-5, 6 and 12 127
Figure. 4.6. OTFT device out-puts of QXN-12 131
Figure. 4.7. AFM image of QXN-12 132
Figure. 5.1. Structure of DCQ derivatives 134
Figure. 5.2. Device structure of PHOLEDs 136
Figure. 5.3. Molecular simulation results of DCQ-1 138
Figure. 5.4. optical spectra of DCQ-1 139
Figure. 5.5. CV of DCQ-1 140
Figure. 5.6. DSC of DCQ-1 141
Figure. 5.7. TGA graph of DCQ-1 141
Figure. 5.8. Current density–voltage curves of hole and electron only devices of DCQ-1 142
Figure. 5.9. (a) Current density-voltage–luminance curves of the yellow PHOLEDs based on DCQ-1 as a function of PO-01 doping concentrations. (b) Current efficiency-luminance curves of the yellow PHOLEDs based on DCQ-1 as a function of PO-01 doping concentrations 144
Figure. 5.10. Quantum efficiency-luminance-power efficiency curves of the yellow PHOLEDs based on DCQ-1 as a function of PO-01 doping concentration 145
Figure. 5.11. EL spectra of the DCQ-1 yellow PHOLEDs according to PO-01 doping concentration 146
List of Schemes
Scheme 2.1. Synthesis of compound 1 to 6 47
Scheme 2.2. Synthesis of compound 7 to 10 47
Scheme 2.3. Synthesis of BTD-1 to BTD-4 48
Scheme 3.1. Synthesis of Br-BTBT-R 77
Scheme 3.2. Synthesis of DIBTBT 78
Scheme 3.3. Synthesis of BTBT-1-BTBT-5 78
Scheme 3.4. Synthesis of BTBT-1 to BTBT-5 78
Scheme 4.1. Synthesis of compounds 11 to 15 120
Scheme 4.2. Synthesis of DBQ, DBDPQ, DBDMOPQ, and DBDTQ 120
Scheme 4.3. Synthesis of compounds QXN-1,2,5,6 and QXN-12 121
Scheme 4.4. Synthesis of QXN-3 and QXN-4 121
Scheme 4.5. Synthesis of QXN-7 and QXN-8 121
Scheme 4.6. Synthesis of QXN-10 to 11 and 13 to 15 122
Scheme 5.1. Synthetic Scheme of DCQ 137
Scheme 6.1. Synthetic Scheme of FMT-1 164
Scheme 6.2. Synthetic Scheme of F-1, F-CN-1 and F-CN-2 165
Scheme 6. 3. Synthetic Scheme of F-2, F-3, F-CN-3 and F-CN-4 166
Scheme 6.4. Synthetic Scheme of F-CN-5 167
Scheme 6.5. Synthetic Scheme of INF-1 and INF-2 168
Scheme 6.6. Synthetic Scheme of INF-1 and INF-3 168
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