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Supporting Information
Novel fluoride-substituted donor/acceptor polymers containing benzodithiophene and quinoxaline units for use in low–band gap solar cells
Ashutosh Singh, Ravinder Singh, Chein-Min Lin, Murali Krishna Pola, Chiao-Kai Chang, Kung-Hwa Wei*, Hong-Cheu Lin*
Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, Taiwan 300.
1. Fig. S1 --------------------------------------------------------------------------------------------------------------------------- page S2
2. Fig S2 ---------------------------------------------------------------------------------------------------------------------------- page S3
3. Fig S3 ---------------------------------------------------------------------------------------------------------------------------- page S4
4. Fig S4 ---------------------------------------------------------------------------------------------------------------------------- page S5
5. Fig S4 ---------------------------------------------------------------------------------------------------------------------------- page S6
6. Table S1 ------------------------------------------------------------------------------------------------------------------------- page S7
7. Table S2 ------------------------------------------------------------------------------------------------------------------------- page S8
8. Table S3 ------------------------------------------------------------------------------------------------------------------------- page S9
9. Table S4 ------------------------------------------------------------------------------------------------------------------------- page S10
10. Fig S5 --------------------------------------------------------------------------------------------------------------------------- page S11
11. 1H-NMR data of intermediate 5 --------------------------------------------------------------------------------------------- page S12
12. 1H-NMR data of intermediate AM1 ---------------------------------------------------------------------------------------- page S13
13. 13C-NMR data of intermediate AM1 --------------------------------------------------------------------------------------- page S14
14. 1H-NMR data of intermediate AM2 ---------------------------------------------------------------------------------------- page S15
15. 1H-NMR data of intermediate AM2 ---------------------------------------------------------------------------------------- page S16
16, 1H-NMR data of polymers------------------------------------------------------------------------------------------------------page S17-20
17. Elementary analysis mass data of AM1 and AM2 ------------------------------------------------------------------------ page S21
18. Elementary analysis mass data of DM1 and DM2 ------------------------------------------------------------------------ page S22
19. Elementary analysis mass data of PTF1, POF1, PTF2, and POF2 ---------------------------------------------------- page S23
S1
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Fig. S1. Basic device structure of the polymer solar cells.
S2
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Fig. S2. FTIR spectra of polymers PTF1, POF1, PTF2, and POF2.
S3
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Fig. S3. XRD data of polymers PTF1, POF1, PTF2, and POF2.
S4
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Fig. S4. TGA and their corresponding thermogravimetric derivative (DTG) data of polymers (a) PTF1, (b) POF1, (c) PTF2, and (d) POF2 at a heating rate of 20 °C/min.
S5
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Fig. S5. DSC data of polymers PTF1, POF1, PTF2, and POF2 at a heating rate of 10 °C/min.
S6
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Table S1 Performances of photovoltaic devices incorporating the polymer PTF1 blended with PC60BM or PC70BM.
PTF1:PC60BM/ PC70BM
RPM/ Concentrationa
[mg mL–1]
Anneal [°C]
Voc [V] Jsc [mA cm–2] FF PCE [%]
PTF1:PC60BM
1:1 in CB 1000/3 X 0.76 2.23 0.25 0.43
1600/3 X 0.54 2.71 0.26 0.39
2400/3 X 0.75 1.36 0.26 0.22
1600/3 90 0.66 2.95 0.3 0.51
2400/4 X 0.68 0.75 0.23 0.12
3200/4 X 0.67 0.1 0.23 0.12
4200/4 X 0.68 0.57 0.25 0.09
1:1.5 in CB 1800/3 X 0.63 2.53 0.30 0.47
800/3 120 0.65 2.03 0.32 0.43
1300/3 120 0.56 2.24 0.29 0.37
1800/3 120 0.57 2.95 0.30 0.51
PTF1:PC70BM
1:1 in CB 1200/3 X 0.75 3.18 0.31 0.74
800/3 120 0.71 2.72 0.32 0.64
1200/3 120 0.69 2.80 0.30 0.58
1800/3 120 0.72 4.97 0.29 1.04
1.5:1 in CB 1000/3 X 0.71 1.59 0.25 0.25
1600/3 X 0.72 1.38 0.21 0.21
2400/3 X 0.53 1.90 0.25 0.26
1600/3 120 0.74 2.07 0.25 0.38
2400/3 120 0.71 2.53 .025 0.45
aTotal concentration of the polymer:PC60BM/PC70BM in solution.
S7
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Table S2 Performances of photovoltaic devices incorporating the polymer POF1 blended with PC60BM or PC70BM.
POF1:PC60BM/ PC70BM
RPM/ Concentrationa
[mg mL–1]
Anneal [°C]
Voc [V] Jsc [mA cm–2] FF PCE [%]
POF1:PC60BM1:1 in CB 800/3 X 0.73 0.60 0.26 0.11
1200/3 X 0.72 0.92 0.25 0.171600/3 X 0.70 1.10 0.24 0.192000/3 X 0.75 1.44 0.25 0.27800/3 X 0.72 1.09 0.23 0.181200/3 X 0.76 1.42 0.24 0.261600/3 X 0.77 2.01 0.24 0.372000/3 X 0.74 2.27 0.26 0.44
1:2 in CB 800/3 X 0.70 2.85 0.26 0.521200/3 X 0.66 2.49 0.29 0.47
1600/3 X 0.73 2.08 0.27 0.412000/3 X 0.58 2.11 0.29 0.36
POF1:PC70BM1:1.5 in CHCl3 1500/3 X 0.72 3.11 0.27 0.61
2000/3 X 0.78 4.42 0.30 1.032500/3 X 0.79 5.17 0.30 1.222000/3 1% DIO 0.75 2.8 0.30 0.632500/3 1% DIO 0.73 1.46 0.27 0.27
aTotal concentration of the polymer:PC60BM/PC70BM in solution.
S8
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Table S3 Performances of photovoltaic devices incorporating the polymer PTF2 blended with PC60BM or PC70BM.
PTF2:PC60BM/ PC70BM
RPM/ Concentrationa
[mg mL–1]
Anneal [°C]
Voc [V] Jsc [mA cm–2] FF PCE [%]
PTF2:PC60BM1:1 in CB 1000/3 X 0.79 3.19 0.33 0.84
1600/3 X 0.59 3.95 0.31 0.912200/3 X 0.77 4.85 0.30 1.121600/3 120 0.75 4.18 0.30 0.95
1:1.5 in CB 1000/3 X 0.73 5.15 0.37 1.391500/3 X 0.72 3.75 0.37 1.012000/3 X 0.72 4.31 0.36 1.102500/3 X 0.60 3.56 0.29 0.62
1:2 in CB 1500/3 X 0.72 5.90 0.35 1.502000/3 100 0.70 6.92 0.36 1.762500/3 X 0.53 4.38 0.34 0.793000/3 X 0.62 4.39 0.41 1.11
PTF2:PC70BM1:1.5 in CB 800/3 X 0.72 3.56 0.35 0.91
1000/3 X 0.71 4.74 0.33 1.121500/3 X 0.70 7.67 0.32 1.722000/3 X 0.72 8.70 0.34 2.131000/3 100 0.72 4.97 0.33 1.19800/3 X 0.72 3.56 0.35 0.911000/3 X 0.71 4.78 0.33 1.121500/3 X 0.70 7.67 0.32 1.722000/3 X 0.72 8.70 0.34 2.131000/3 100 0.72 4.97 0.33 1.191500/3 1% DIO 0.51 2.76 0.30 0.422000/3 1% DIO 0.03 2.38 0.21 0.012500/3 1% DIO 0.70 0.04 0.25 0.011500/3 X 0.71 5.2 0.35 1.31800/3 X 0.71 6.24 0.34 1.522000/3 X 0.77 4.91 0.33 1.242000/3 X 0.77 5.72 0.33 1.472000/3 100C 10 M 0.76 5.79 0.33 1.462000/3 120C 10 M 0.74 6.22 0.33 1.542000/3 150C 10 M 0.71 5.12 0.33 1.19
aTotal concentration of the polymer:PC60BM/PC70BM in solution.
S9
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Table S4 Performances of photovoltaic devices incorporating the polymer POF2 blended with PC60BM or PC70BM.
POF2:PC60BM/ PC70BM
RPM/ Concentrationa
[mg mL–1]
Anneal [°C]
Voc [V] Jsc [mA cm–2] FF PCE [%]
POF2:PC60BM1:1 in CHCl3 1000/1.5 X 0.71 2.20 0.25 0.39
2000/1.5 X 0.71 2.82 0.26 0.533500/1.5 X 0.68 3.10 0.27 0.572000/1.5 120 0.70 2.27 0.32 0.511200/1 X 0.77 5.33 0.34 1.411800/1 X 0.77 5.49 0.33 1.401000/1 120 0.74 3.22 0.31 0.741200/1 120 0.72 4.97 0.33 1.19
1:1.5 in CHCl3 800/1 X 0.79 4.26 0.33 1.111200/1 X 0.77 4.58 0.34 1.182000/1 X 0.77 4.16 0.35 1.12
1:1.5 in CB 800/1 X 0.77 5.06 0.34 1.311200/1 X 0.67 4.50 0.33 1.002000/1 X 0.49 3.89 0.30 0.581200/1 120 0.66 5.29 0.36 1.25
1:2 in CHCl3 1200/1 X 0.76 3.58 0.37 1.021800/1 X 0.76 3.38 0.39 1.001000/1 120 0.71 3.87 0.30 0.831200/1 120 0.76 4.28 0.32 1.05
POF2:PC70BM1:1.5 in CHCl3 1000/1 X 0.76 3.89 0.40 1.18
2000/1 X 0.77 5.25 0.40 1.601000/1 120 0.75 4.83 0.32 1.182000/1 120 0.76 4.87 0.32 1.18
1:1.5 in CB 2500/3 X 0.77 3.87 0.31 0.912000/3 X 0.76 3.19 0.30 0.721500/3 X 0.77 2.89 0.30 0.672500/3 1% DIO strange2000/3 1% DIO 0.80 4.56 0.41 1.481500/3 1% DIO 0.80 5.19 0.31 1.30
aTotal concentration of the polymer:PC60BM/PC70BM in solution.
S10
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Fig. S6. SEM images of blends of the polymers (a) PTF1, (b) POF1, (c) PTF2, and (d) POF2 with PC70BM (1:1.5, w/w).
S11
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1H NMR of 5,5´-(5,8-Dibromoquinoxaline-2,3-diyl)bis(1H-pyrrole-2-carbaldehyde) (5)
S12
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1H NMR of (N,N´E,N,N´E)-N,N´-((5,5´-(5,8-dibromoquinoxaline-2,3-diyl)bis(1H-pyrrole-5,2-diyl)) bis (methanylylidene))bis(2-fluoroaniline) (AM1)
S13
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13C NMR of (N,N´E,N,N´E)-N,N´-((5,5´-(5,8-dibromoquinoxaline-2,3-diyl)bis(1H-pyrrole-5,2-diyl)) bis (methanylylidene))bis(2-fluoroaniline) (AM1)
S14
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1H NMR of (N,N´E,N,N´E)-N,N´-((5,5´-(5,8-dibromoquinoxaline-2,3-diyl)bis(1H-pyrrole-5,2diyl))bis(methanylylidene))bis(2,6-difluoroaniline) (AM2)
S15
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13C NMR of (N,N´E,N,N´E)-N,N´-((5,5´-(5,8-dibromoquinoxaline-2,3-diyl)bis(1H-pyrrole-5,2diyl))bis(methanylylidene))bis(2,6-difluoroaniline) (AM2)
S16
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1H NMR of polymer PTF1
S17
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1H NMR of polymer POF1
S18
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1H NMR of polymer PTF2
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1H NMR of polymer POF2
S20
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Elementary analysis mass data of acceptor monomers AM1 and AM2 (i.e., solar F1 and solar F2, respectively)
S21
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Elementary analysis mass data of donor monomers DM1 and DM2.
S22
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Elementary analysis mass data of polymers PTF1, POF1, PTF2, and POF2 (i.e., THF1-P, OCF1-P, THF2-P, and OCF2-P, respectively)
S23