Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2013.
Supporting Information for Adv. Mater., DOI: 10.1002/adma.201303586
Dithienocarbazole and Isoindigo based Amorphous Low Bandgap Conjugated Polymers for Efficient Polymer Solar Cells Yunfeng Deng, Jian Liu, Jiantai Wang, Lihui Liu, Weili Li, Hongkun Tian, Xiaojie Zhang, Zhiyuan Xie,* Yanhou Geng,* and Fosong Wang
Submitted to
Supporting Information for Dithienocarbazole and Isoindigo based Amorphous Low Bandgap Conjugated Polymers for Efficient Polymer Solar Cells
By Yunfeng Deng, Jian Liu, Jiantai Wang, Lihui Liu, Weili Li, Hongkun Tian, Xiaojie Zhang, Zhiyuan Xie,* Yanhou Geng,* and Fosong Wang ((Optional Dedication)) [*]
Prof. Y. H. Geng, Prof. Z. Y. Xie, Y. F. Deng, J. Liu, J. T. Wang, L. H. Liu, W. L. Li,
Dr. H. K. Tian, Dr. X. J. Zhang, Prof. F. S. Wang State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun 130022 (P. R. China) E-mail: [email protected], [email protected] Y. F. Deng, J. Liu, J. T. Wang, L. H. Liu University of Chinese Academy of Sciences Beijing 100049 (P. R. China)
Contents 1. Synthesis 2. Figure S1. TGA plots of the polymers 3. Figure S2. DSC curves of the polymer 4. Figure S3. Solution absorption spectra of the polymers 5. Figure S4. Typical output and transfer characteristics of OTFT devices 6. Figure S5. J-V characteristics of the hole only devices of the neat polymers 7. Figure S6. J-V characteristics of the hole only and electron only devices of the P(IIDDTC)/PC71BM bends with different weight ratios 8. Table S1. Hole and electron mobilities of P(IID-DTC)/PC71BM blends 9. Figure S7. J-V curves and EQE profiles of the conventional devices based on P(IIDDTC) with different D/A ratios 10. Table S2. Performance of the conventional devices based on P(IID-DTC) with different D/A ratios 11. Figure S8. J-V curves and EQE profiles of the conventional devices based on P(IID1F1
Submitted to DTC) with different D/A ratios 12. Table S4. Performance of the conventional devices based on P(IID1F-DTC) with different D/A ratios 13. Figure S9. J-V curves and EQE of the conventional devices based on P(IID1F-DTC) with different thickness 14. Table S5. Performance of the conventional devices based on P(IID1F-DTC) with different thickness 15. Figure S10. J-V curves and EQE profiles of the conventional devices based on P(IID2FDTC) with different D/A ratios 16. Table S6. Performance of the conventional devices based on P(IID2F-DTC) with different D/A ratios 17. Figure S11. TEM images of P(IID-DTC)/PC71BM films with different weight ratios 18. Figure S12. TEM images of P(IID1F-DTC)/PC71BM films with different weight ratios 19. Figure S13. TEM images of P(IID2F-DTC)/PC71BM films with different weight ratios 20. Figure S14. Thin film XRD profiles of the neat polymers and blend films 21. Figure S15. Electron diffraction pattern of the blend films 22. Spectral mismatch factor of the light source
2
Submitted to Materials and Synthesis THF and toluene were distilled over sodium/benzophenone. Et3N, acetonitrile and CH2Cl2 were distilled after drying with CaH2. Synthesis of organotin reagents of dithieno[3,2-b;6,7b]carbazole were reported elseshere[1]. 6,6’-dibromo-N,N’-(2-octyldodecanyl)-isoindigo[2] and 6,6’-dibromo-7,7’- difluoro-N,N’-(2-octyldodecanyl)-isoindigo[3] were synthesized according to literature report. Other reagents were obtained from commercial resources and used without further purification. The synthesis of polymers were according to the report previously[4].
Scheme S1. The synthesis 6,6’-dibromo-7-fluoro-N,N’-(2-octyldodecanyl)-isoindigo and polymers.
6,6’-Dibromo-7-fluoroisoindigo (3).To a suspension of 1 (4.0 g, 16.39 mmol) and 2 (3.48 g, 16.39 mmol) in AcOH (200 mL) was added conc. HCl (37%) solution (1.2 mL). The mixture was refluxed for 24 hrs, and then was cooled to room temperature and filtered. The solid was washed with water, ethanol and ether in succession. After drying under vacuum, the compound 3 was obtained as a deep red solid (5.1 g, 70%). 1H NMR (DMSO-d6, 400 MHz, ppm): δ 11.62 (s, 1H), 11.08 (s, 1H), 8.96 (d, 2H), 8.82 (d, 2H), 7.24-7.27 (dd, 1H), 7.16-7.18 (dd, 1H), 6.96 (s, 1H). 6,6’-Dibromo-7-fluoro-N,N’-(2-octyldodecanyl)-isoindigo (4). To a solution of 6,6’dibromo-7-fluoroisoindigo (3) (700 mg,1.6 mmol) and freshly powered KOH (358.6 mg, 6.39 3
Submitted to mmol) in dimethyl sulfoxide (DMSO) (30 mL) was added 9-iodomethylnonadecane (2.61 g, 6.39 mmol) in THF (30 mL) was added under nitrogen. The mixture was stirred for 24 hrs at 25 oC before pouring into water. The mixture was extracted with CHCl3. The combined organic phase was washed with brine and dried with MgSO4 and concentrated under reduced pressure. The residue was purified by silica gel chromatography with eluting (PE: CH2Cl2 = 8:1) to give 4 as a deep-red solid. (672 mg, 42 %).1H NMR (CDCl3, 400 MHz, ppm): δ 9.04 (d, 1H), 8.92 (d, 1H), 7.16-7.26 (m, 2H), 6.90 (s, 1H), 3.83 (d, 2H), 3.62 (d, 2H), 1.88 (m, 2H), 1.23 (m, 64H), 0.86 (t, 12H). General procedure for the synthesis of polymers. In an air-free flask charged with the two monomers (0.3 mmol, each, 1:1 mol/mol), Pd2(dba)3 (0.02 equiv, 2% mol), and P(o-tolyl)3 (0.16 equiv 8% mol) was added anhydrous toluene (20 ml) via syringe. The sealed reaction mixture was stirred at 120 ºC for 48 hrs. Then 4bromotoluene (20.6 mg, 0.12 mmol) was added and the reaction was continued for another 12 hrs. After cooling to room temperature, the deep blue mixture was dropped into 300 mL of methanol with vigorous stirring, and then the crude polymer was collected by filtration. After drying,
the
residual
catalyst
was
removed
by
treating
with
sodium
diethyldithiocarbamatetrihydrate in dichlorobenzene (100 ml) at 80 oC for 12 hrs. The mixture was washed with water and dried with anhydrous MgSO4. The polymer solution was concentrated to approximately 20 mL, precipitated in methanol, and then extracted on a Soxhlet’s extractor with acetone, hexane and then chloroform. P(IID-DTC): blue power, 94.8% yield. (C84H121N3O2S2)n (1267.89): Calcd. C, 79.50; H, 9.61; N, 3.31. Found C, 79.08; H, 9.36; N, 3.01. P(IID1F-DTC): blue power, 82.5% yield, (C84H120FN3O2S2)n (1285.88): Calcd. C, 78.39; H, 9.40; N, 3.26. Found C, 77.91; H, 8.97; N, 3.07 P(IID2F-DTC): blue power, 78.2% yield, (C84H119F2N3O2S2)n(1303.87): Calcd. C, 77.31; H, 9.19; N, 3.22. Found C, 76.89; H, 8.89; N, 2.91. 4
Submitted to Instruments. 1H spectra were recorded on a Bruker 400-MHz spectrometer in CDCl3. Chemical shift was reported relative to an internal tetramethylsilane (TMS) standard for the measurements with CDCl3 or DMSO as solvent. UV-vis absorption was recorded on a Shimadzu UV-3600 UV-vis-NIR spectrometer. The bandgap was calculated according to the onset absorption of UV-vis spectra (Eg = 1240/λonset eV). High temperature GPC analysis was conducted on a PL-GPC 220 system using polystyrene as standard and 1, 2, 4trichlorobenzene as eluent at 150 oC. Thermogravimetric analysis (TGA) was carried out on a Perkin-Elmer TGA7 at a heating rate of 10 °C·min–1 under nitrogen flow. Differential scanning calorimetry (DSC) was performed on a Perkin-Elmer DSC 7 with a heating/cooling rate of 10/-10 oC·min–1 under nitrogen flow. Film CV was performed on a CHI660a electrochemical analyzer with a three-electrode cell at a scan rate of 100 mV·s-1. Bu4NPF6 (0.1 mol·L-1) was used as electrolyte. Anhydrous acetonitrile was used as the solvent. A glassy carbon electrode with a diameter of 10 mm, a Pt wire, and a saturated calomel electrode were used as the working, counter, and reference electrodes, respectively. To obtain electronic energy levels of the polymer films, the occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were estimated by the equations: ox re HOMO = – (4.80+ Eonset ) eV, LUMO= – (4.80+ Eonset ) eV.
Reference: [1] Y. G. Chen, C. F. Liu, H. K. Tian, C. Bao, X. J. Zhang, D. H. Yan, Y. H. Geng, F. S. Wang, Macromol. Rapid Commun. 2012, 33, 1759. [2] T. Lei, Y. Cao, Y. L. Fan, C-J. Liu, S-C. Yuan, J. Pei, J. Am. Chem. Soc. 2011, 133, 6099. [3] T. Lei, J-H. Dou, Z-J. Ma, C-H. Yao, C-J. Liu, J-Y. Wang, J. Pei, J. Am. Chem. Soc. 2012, 134, 20025. [4] Y. F. Deng, Y. G. Chen, J. Liu, L. H. Liu, H. K. Tian, Z. Y. Xie, Y. H. Geng, F. S. Wang, ACS Appl. Mater. Interfaces 2013, 5, 5741. 5
Submitted to
Figure S1. TGA plots of the polymers
Figure S2. DSC curves of the polymers. (a) P(IID-DTC); (b) P(IID1F-DTC); (c) P(IID2FDTC)
6
Submitted to
Figure S3. Absorption spectra of the polymers in o-dichlorobenzene
Figure S4. Typical output (a, c) and transfer (b, d) characteristics of OTFT devices of P(IID1F-DTC) (a, b) and P(IID2F-DTC) (c, d).
7
Submitted to
Figure S5. J-V characteristics measured under dark for hole only devices of the neat polymers. Lines represent the fitting results using a model of single-carrier space-charge-limited current with field-dependent mobility.
Figure S6. J-V characteristics measured under dark for (a) hole only and (b) electron only devices of the P(IID-DTC)/PC71BM films with different weight ratios. Lines represent the fitting results using a model of single-carrier space-charge-limited current with fielddependent mobility. Table S1. The hole and electron mobilities of P(IID-DTC)/PC71BM blends measured by SCLC method. Ratio 1:1 1:2 1:3 1:4
Hole mobility (cm2/V-1s-1) 4.36 × 10-4 2.81 × 10-4 2.11 × 10-4 2.09 × 10-4
8
Electron mobility (cm2/V-1s-1) 1.73 × 10-3 2.57 × 10-3 3.54 × 10-3 3.82 × 10-3
Submitted to
Figure S7. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IIDDTC) with different D/A ratios.
Table S2. Photovoltaic characteristics of the conventional devices based on P(IID-DTC) with different D/A ratios under the AM 1.5G illumination at 100 mW cm-2 Ratio 1:1 1:1.5 1:2 1:2.5 1:3 1:4
Voc(V) 0.79 0.77 0.79 0.78 0.73 0.75
J sc(mA/cm2) 13.2 13.7 14.3 12.9 12.2 9.9
9
FF 0.55 0.58 0.62 0.61 0.57 0.56
PCE 5.8 6.11 7.0 6.2 5.1 4.2
Submitted to
Figure S8. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IID1F-DTC) with different D/A ratios.
Table S3. Photovoltaic characteristics of the conventional devices based on P(IID1F-DTC) with different D/A ratios under the AM 1.5G illumination at 100 mW cm-2 Ratio 1:1 1:1.5 1:2 1:2.5 1:3 1:4
Voc(V) 0.86 0.85 0.82 0.82 0.81 0.79
Jsc (mA/cm2) 11.5 12.4 12.0 11.1 10.6 8.9
FF 0.50 0.54 0.64 0.63 0.65 0.62
10
PCE 4.9 5.9 6.3 5.7 5.5 4.4
Submitted to
Figure S9. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IID1F-DTC) with different thickness, 1% DIO was added into o-DCB as an additive.
Table S4. Photovoltaic characteristics of the conventional devices based on P(IID1F-DTC) with different thickness under the AM 1.5G illumination at 100 mW cm-2 Thickness(nm) 213 163 125 117 102
Voc (V) 0.78 0.81 0.82 0.83 0.83
Jsc(mA/cm2) 14.2 13.4 12.3 12.4 12.6
FF 0.48 0.56 0.65 0.66 0.68
11
PCE 5.3 6.2 6.6 6.8 7.1
Submitted to
Figure S10. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IID2F-DTC) with different D/A ratios.
Table S5. Photovoltaic characteristics of the conventional devices based on P(IID2F-DTC) with different D/A ratios under the AM 1.5G illumination at 100 mW cm-2 Ratio 1:1 1:2 1:3 1:4
Voc 0.91 0.86 0.85 0.86
Jsc 11.3 12.6 12.7 9.1
FF 0.57 0.63 0.51 0.64
12
PCE 5.9 6.8 5.5 5.1
Submitted to
Figure S11. TEM images of P(IID-DTC)/PC71BM films with different weight ratios. (a) 1:1; (b) 1:2; (c) 1:3; (d) 1:4.
Figure S12. TEM images of P(IID1F-DTC)/PC71BM films with different weight ratios. (a) 1:1; (b) 1:2; (c) 1:3; (d) 1:4.
13
Submitted to
Figure S13. TEM images of P(IID2F-DTC)/PC71BM films with different weight ratios. (a) 1:1; (b) 1:2; (c) 1:3; (d) 1:4.
14
Submitted to
Figure S14. Thin film XRD of the neat polymers (a), P(IID-DTC)/PC71BM blends (b), P(IID1F-DTC)/PC71BM blends (c), and P(IID2F-DTC)/PC71BM blends (d).
Figure S15. Electron diffraction patterns of P(IID-DTC) (a), P(IID1F-DTC) (b), and P(IID2F-DTC) (c). 1% DIO was added into solvent o-DCB in the preparation of the blend films based on P(IID1F-DTC) and P(IID2F-DTC).
15
Submitted to Table S7. Spectral mismatch factor Test cell
Mismatch factor
P(IIDP(IIDDTC) DTC ) conventional inverted 1.0487
1.0512
P(IID1FP(IID1FDTC) DTC ) conventional inverted 1.0568
1.0543
P(IID2FP(IID2FDTC) DTC) conventional inverted 1.0680
1.0616
Spectral mismatch factor was calculated according ref. : V. Shrotriya, G. Li, Y. Yao, T. Moriarty, K. Emery, Y. Yang, Adv. Funct. Mater. 2006, 16, 2016.
16
Submitted to Comparison between the data measured in our lab and Changchun Institute of Optics, Fine Mechanics and Physics (CIOFM), Chinese Academy of Sciences.
4
2
JSC (mA/cm )
0 Tested in our lab Tested in other lab
-4 -8
-12 -16 0.0
0.2
0.4 0.6 VOC (V)
0.8
1.0
VOC (V)
JSC (mA/cm2)
FF
PCE (%)
In our lab
0.78
15.0
0.68
8.0
In CIOFM
0.80
14.5
0.66
7.7
17
Supporting Information for Adv. Mater., DOI: 10.1002/adma.201303586
Dithienocarbazole and Isoindigo based Amorphous Low Bandgap Conjugated Polymers for Efficient Polymer Solar Cells Yunfeng Deng, Jian Liu, Jiantai Wang, Lihui Liu, Weili Li, Hongkun Tian, Xiaojie Zhang, Zhiyuan Xie,* Yanhou Geng,* and Fosong Wang
Submitted to
Supporting Information for Dithienocarbazole and Isoindigo based Amorphous Low Bandgap Conjugated Polymers for Efficient Polymer Solar Cells
By Yunfeng Deng, Jian Liu, Jiantai Wang, Lihui Liu, Weili Li, Hongkun Tian, Xiaojie Zhang, Zhiyuan Xie,* Yanhou Geng,* and Fosong Wang ((Optional Dedication)) [*]
Prof. Y. H. Geng, Prof. Z. Y. Xie, Y. F. Deng, J. Liu, J. T. Wang, L. H. Liu, W. L. Li,
Dr. H. K. Tian, Dr. X. J. Zhang, Prof. F. S. Wang State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun 130022 (P. R. China) E-mail: [email protected], [email protected] Y. F. Deng, J. Liu, J. T. Wang, L. H. Liu University of Chinese Academy of Sciences Beijing 100049 (P. R. China)
Contents 1. Synthesis 2. Figure S1. TGA plots of the polymers 3. Figure S2. DSC curves of the polymer 4. Figure S3. Solution absorption spectra of the polymers 5. Figure S4. Typical output and transfer characteristics of OTFT devices 6. Figure S5. J-V characteristics of the hole only devices of the neat polymers 7. Figure S6. J-V characteristics of the hole only and electron only devices of the P(IIDDTC)/PC71BM bends with different weight ratios 8. Table S1. Hole and electron mobilities of P(IID-DTC)/PC71BM blends 9. Figure S7. J-V curves and EQE profiles of the conventional devices based on P(IIDDTC) with different D/A ratios 10. Table S2. Performance of the conventional devices based on P(IID-DTC) with different D/A ratios 11. Figure S8. J-V curves and EQE profiles of the conventional devices based on P(IID1F1
Submitted to DTC) with different D/A ratios 12. Table S4. Performance of the conventional devices based on P(IID1F-DTC) with different D/A ratios 13. Figure S9. J-V curves and EQE of the conventional devices based on P(IID1F-DTC) with different thickness 14. Table S5. Performance of the conventional devices based on P(IID1F-DTC) with different thickness 15. Figure S10. J-V curves and EQE profiles of the conventional devices based on P(IID2FDTC) with different D/A ratios 16. Table S6. Performance of the conventional devices based on P(IID2F-DTC) with different D/A ratios 17. Figure S11. TEM images of P(IID-DTC)/PC71BM films with different weight ratios 18. Figure S12. TEM images of P(IID1F-DTC)/PC71BM films with different weight ratios 19. Figure S13. TEM images of P(IID2F-DTC)/PC71BM films with different weight ratios 20. Figure S14. Thin film XRD profiles of the neat polymers and blend films 21. Figure S15. Electron diffraction pattern of the blend films 22. Spectral mismatch factor of the light source
2
Submitted to Materials and Synthesis THF and toluene were distilled over sodium/benzophenone. Et3N, acetonitrile and CH2Cl2 were distilled after drying with CaH2. Synthesis of organotin reagents of dithieno[3,2-b;6,7b]carbazole were reported elseshere[1]. 6,6’-dibromo-N,N’-(2-octyldodecanyl)-isoindigo[2] and 6,6’-dibromo-7,7’- difluoro-N,N’-(2-octyldodecanyl)-isoindigo[3] were synthesized according to literature report. Other reagents were obtained from commercial resources and used without further purification. The synthesis of polymers were according to the report previously[4].
Scheme S1. The synthesis 6,6’-dibromo-7-fluoro-N,N’-(2-octyldodecanyl)-isoindigo and polymers.
6,6’-Dibromo-7-fluoroisoindigo (3).To a suspension of 1 (4.0 g, 16.39 mmol) and 2 (3.48 g, 16.39 mmol) in AcOH (200 mL) was added conc. HCl (37%) solution (1.2 mL). The mixture was refluxed for 24 hrs, and then was cooled to room temperature and filtered. The solid was washed with water, ethanol and ether in succession. After drying under vacuum, the compound 3 was obtained as a deep red solid (5.1 g, 70%). 1H NMR (DMSO-d6, 400 MHz, ppm): δ 11.62 (s, 1H), 11.08 (s, 1H), 8.96 (d, 2H), 8.82 (d, 2H), 7.24-7.27 (dd, 1H), 7.16-7.18 (dd, 1H), 6.96 (s, 1H). 6,6’-Dibromo-7-fluoro-N,N’-(2-octyldodecanyl)-isoindigo (4). To a solution of 6,6’dibromo-7-fluoroisoindigo (3) (700 mg,1.6 mmol) and freshly powered KOH (358.6 mg, 6.39 3
Submitted to mmol) in dimethyl sulfoxide (DMSO) (30 mL) was added 9-iodomethylnonadecane (2.61 g, 6.39 mmol) in THF (30 mL) was added under nitrogen. The mixture was stirred for 24 hrs at 25 oC before pouring into water. The mixture was extracted with CHCl3. The combined organic phase was washed with brine and dried with MgSO4 and concentrated under reduced pressure. The residue was purified by silica gel chromatography with eluting (PE: CH2Cl2 = 8:1) to give 4 as a deep-red solid. (672 mg, 42 %).1H NMR (CDCl3, 400 MHz, ppm): δ 9.04 (d, 1H), 8.92 (d, 1H), 7.16-7.26 (m, 2H), 6.90 (s, 1H), 3.83 (d, 2H), 3.62 (d, 2H), 1.88 (m, 2H), 1.23 (m, 64H), 0.86 (t, 12H). General procedure for the synthesis of polymers. In an air-free flask charged with the two monomers (0.3 mmol, each, 1:1 mol/mol), Pd2(dba)3 (0.02 equiv, 2% mol), and P(o-tolyl)3 (0.16 equiv 8% mol) was added anhydrous toluene (20 ml) via syringe. The sealed reaction mixture was stirred at 120 ºC for 48 hrs. Then 4bromotoluene (20.6 mg, 0.12 mmol) was added and the reaction was continued for another 12 hrs. After cooling to room temperature, the deep blue mixture was dropped into 300 mL of methanol with vigorous stirring, and then the crude polymer was collected by filtration. After drying,
the
residual
catalyst
was
removed
by
treating
with
sodium
diethyldithiocarbamatetrihydrate in dichlorobenzene (100 ml) at 80 oC for 12 hrs. The mixture was washed with water and dried with anhydrous MgSO4. The polymer solution was concentrated to approximately 20 mL, precipitated in methanol, and then extracted on a Soxhlet’s extractor with acetone, hexane and then chloroform. P(IID-DTC): blue power, 94.8% yield. (C84H121N3O2S2)n (1267.89): Calcd. C, 79.50; H, 9.61; N, 3.31. Found C, 79.08; H, 9.36; N, 3.01. P(IID1F-DTC): blue power, 82.5% yield, (C84H120FN3O2S2)n (1285.88): Calcd. C, 78.39; H, 9.40; N, 3.26. Found C, 77.91; H, 8.97; N, 3.07 P(IID2F-DTC): blue power, 78.2% yield, (C84H119F2N3O2S2)n(1303.87): Calcd. C, 77.31; H, 9.19; N, 3.22. Found C, 76.89; H, 8.89; N, 2.91. 4
Submitted to Instruments. 1H spectra were recorded on a Bruker 400-MHz spectrometer in CDCl3. Chemical shift was reported relative to an internal tetramethylsilane (TMS) standard for the measurements with CDCl3 or DMSO as solvent. UV-vis absorption was recorded on a Shimadzu UV-3600 UV-vis-NIR spectrometer. The bandgap was calculated according to the onset absorption of UV-vis spectra (Eg = 1240/λonset eV). High temperature GPC analysis was conducted on a PL-GPC 220 system using polystyrene as standard and 1, 2, 4trichlorobenzene as eluent at 150 oC. Thermogravimetric analysis (TGA) was carried out on a Perkin-Elmer TGA7 at a heating rate of 10 °C·min–1 under nitrogen flow. Differential scanning calorimetry (DSC) was performed on a Perkin-Elmer DSC 7 with a heating/cooling rate of 10/-10 oC·min–1 under nitrogen flow. Film CV was performed on a CHI660a electrochemical analyzer with a three-electrode cell at a scan rate of 100 mV·s-1. Bu4NPF6 (0.1 mol·L-1) was used as electrolyte. Anhydrous acetonitrile was used as the solvent. A glassy carbon electrode with a diameter of 10 mm, a Pt wire, and a saturated calomel electrode were used as the working, counter, and reference electrodes, respectively. To obtain electronic energy levels of the polymer films, the occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were estimated by the equations: ox re HOMO = – (4.80+ Eonset ) eV, LUMO= – (4.80+ Eonset ) eV.
Reference: [1] Y. G. Chen, C. F. Liu, H. K. Tian, C. Bao, X. J. Zhang, D. H. Yan, Y. H. Geng, F. S. Wang, Macromol. Rapid Commun. 2012, 33, 1759. [2] T. Lei, Y. Cao, Y. L. Fan, C-J. Liu, S-C. Yuan, J. Pei, J. Am. Chem. Soc. 2011, 133, 6099. [3] T. Lei, J-H. Dou, Z-J. Ma, C-H. Yao, C-J. Liu, J-Y. Wang, J. Pei, J. Am. Chem. Soc. 2012, 134, 20025. [4] Y. F. Deng, Y. G. Chen, J. Liu, L. H. Liu, H. K. Tian, Z. Y. Xie, Y. H. Geng, F. S. Wang, ACS Appl. Mater. Interfaces 2013, 5, 5741. 5
Submitted to
Figure S1. TGA plots of the polymers
Figure S2. DSC curves of the polymers. (a) P(IID-DTC); (b) P(IID1F-DTC); (c) P(IID2FDTC)
6
Submitted to
Figure S3. Absorption spectra of the polymers in o-dichlorobenzene
Figure S4. Typical output (a, c) and transfer (b, d) characteristics of OTFT devices of P(IID1F-DTC) (a, b) and P(IID2F-DTC) (c, d).
7
Submitted to
Figure S5. J-V characteristics measured under dark for hole only devices of the neat polymers. Lines represent the fitting results using a model of single-carrier space-charge-limited current with field-dependent mobility.
Figure S6. J-V characteristics measured under dark for (a) hole only and (b) electron only devices of the P(IID-DTC)/PC71BM films with different weight ratios. Lines represent the fitting results using a model of single-carrier space-charge-limited current with fielddependent mobility. Table S1. The hole and electron mobilities of P(IID-DTC)/PC71BM blends measured by SCLC method. Ratio 1:1 1:2 1:3 1:4
Hole mobility (cm2/V-1s-1) 4.36 × 10-4 2.81 × 10-4 2.11 × 10-4 2.09 × 10-4
8
Electron mobility (cm2/V-1s-1) 1.73 × 10-3 2.57 × 10-3 3.54 × 10-3 3.82 × 10-3
Submitted to
Figure S7. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IIDDTC) with different D/A ratios.
Table S2. Photovoltaic characteristics of the conventional devices based on P(IID-DTC) with different D/A ratios under the AM 1.5G illumination at 100 mW cm-2 Ratio 1:1 1:1.5 1:2 1:2.5 1:3 1:4
Voc(V) 0.79 0.77 0.79 0.78 0.73 0.75
J sc(mA/cm2) 13.2 13.7 14.3 12.9 12.2 9.9
9
FF 0.55 0.58 0.62 0.61 0.57 0.56
PCE 5.8 6.11 7.0 6.2 5.1 4.2
Submitted to
Figure S8. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IID1F-DTC) with different D/A ratios.
Table S3. Photovoltaic characteristics of the conventional devices based on P(IID1F-DTC) with different D/A ratios under the AM 1.5G illumination at 100 mW cm-2 Ratio 1:1 1:1.5 1:2 1:2.5 1:3 1:4
Voc(V) 0.86 0.85 0.82 0.82 0.81 0.79
Jsc (mA/cm2) 11.5 12.4 12.0 11.1 10.6 8.9
FF 0.50 0.54 0.64 0.63 0.65 0.62
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PCE 4.9 5.9 6.3 5.7 5.5 4.4
Submitted to
Figure S9. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IID1F-DTC) with different thickness, 1% DIO was added into o-DCB as an additive.
Table S4. Photovoltaic characteristics of the conventional devices based on P(IID1F-DTC) with different thickness under the AM 1.5G illumination at 100 mW cm-2 Thickness(nm) 213 163 125 117 102
Voc (V) 0.78 0.81 0.82 0.83 0.83
Jsc(mA/cm2) 14.2 13.4 12.3 12.4 12.6
FF 0.48 0.56 0.65 0.66 0.68
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PCE 5.3 6.2 6.6 6.8 7.1
Submitted to
Figure S10. J-V curves (a) and EQE profiles (b) of the conventional devices based on P(IID2F-DTC) with different D/A ratios.
Table S5. Photovoltaic characteristics of the conventional devices based on P(IID2F-DTC) with different D/A ratios under the AM 1.5G illumination at 100 mW cm-2 Ratio 1:1 1:2 1:3 1:4
Voc 0.91 0.86 0.85 0.86
Jsc 11.3 12.6 12.7 9.1
FF 0.57 0.63 0.51 0.64
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PCE 5.9 6.8 5.5 5.1
Submitted to
Figure S11. TEM images of P(IID-DTC)/PC71BM films with different weight ratios. (a) 1:1; (b) 1:2; (c) 1:3; (d) 1:4.
Figure S12. TEM images of P(IID1F-DTC)/PC71BM films with different weight ratios. (a) 1:1; (b) 1:2; (c) 1:3; (d) 1:4.
13
Submitted to
Figure S13. TEM images of P(IID2F-DTC)/PC71BM films with different weight ratios. (a) 1:1; (b) 1:2; (c) 1:3; (d) 1:4.
14
Submitted to
Figure S14. Thin film XRD of the neat polymers (a), P(IID-DTC)/PC71BM blends (b), P(IID1F-DTC)/PC71BM blends (c), and P(IID2F-DTC)/PC71BM blends (d).
Figure S15. Electron diffraction patterns of P(IID-DTC) (a), P(IID1F-DTC) (b), and P(IID2F-DTC) (c). 1% DIO was added into solvent o-DCB in the preparation of the blend films based on P(IID1F-DTC) and P(IID2F-DTC).
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Submitted to Table S7. Spectral mismatch factor Test cell
Mismatch factor
P(IIDP(IIDDTC) DTC ) conventional inverted 1.0487
1.0512
P(IID1FP(IID1FDTC) DTC ) conventional inverted 1.0568
1.0543
P(IID2FP(IID2FDTC) DTC) conventional inverted 1.0680
1.0616
Spectral mismatch factor was calculated according ref. : V. Shrotriya, G. Li, Y. Yao, T. Moriarty, K. Emery, Y. Yang, Adv. Funct. Mater. 2006, 16, 2016.
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Submitted to Comparison between the data measured in our lab and Changchun Institute of Optics, Fine Mechanics and Physics (CIOFM), Chinese Academy of Sciences.
4
2
JSC (mA/cm )
0 Tested in our lab Tested in other lab
-4 -8
-12 -16 0.0
0.2
0.4 0.6 VOC (V)
0.8
1.0
VOC (V)
JSC (mA/cm2)
FF
PCE (%)
In our lab
0.78
15.0
0.68
8.0
In CIOFM
0.80
14.5
0.66
7.7
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