SUPPORTING INFORMATION. A Series of Simple Oligomer-like Small Molecules Based on. Oligothiophenes for Solution-Processed Solar Cells with High

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1 SUPPORTING INFORMATION A Series of Simple Oligomer-like Small Molecules Based on Oligothiophenes for Solution-Processed Solar Cells with High Efficiency Bin Kan 1, Miaomiao Li 1, Qian Zhang 1, Feng Liu 2, Xiangjian Wan 1, Yunchuang Wang 1, Wang Ni 1, Guankui Long 1, Xuan Yang 1, Huanran Feng 1, Yi Zuo 1, Mingtao Zhang 4, Fei Huang 3, Yong Cao 3, Thomas P. Russell 2, Yongsheng Chen 1 * 1 State Key Laboratory and Institute of Elemento-Organic Chemistry and Centre for Nanoscale Science and Technology, Institute of Polymer Chemistry and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin, , China 2 Polymer Science and Engineering Department, University of Massachusetts, Amherst, MA 0103, USA 3 State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, , China 4 Computational Center for Molecular Science, College of Chemistry, Nankai University, Tianjin, , China Corresponding author: yschen99@nankai.edu.cn (YC) S1

2 1. Materials and measurements. 2. Synthesis Synthesis of compound DRCN4T Synthesis of compound DRCN5T Synthesis of compound DRCN6T Synthesis of compound DRCN8T Synthesis of compound DRCN9T. 3. The calculation results. Figure S1. The optimized geometries for DRCN4T-DRCN9T. Table S1. The calculation results of dipole moment. 4. Thermogravimetric and DSC thermograms. Figure S2. a) TGA plot of DRCN4T-DRCN9T with a heating rate of 10 o C min -1 under N 2 atmosphere. b) DSC thermograms of DRCN4T-DRCN9T at a temperature ramp rate of 10 o C min -1 under N 2. Table S2. The thermal properties data of DRCN4T-DRCN9T. 5. Cyclic voltammograms. Figure S3. Cyclic voltammograms of DRCN4T-DRCN9T. Table S3. Electrochemical and calculation data of DRCN4T-DRCN9T. 6. Morphology analysis. Figure S4. Atomic force microscopy images of DRCN4T-DRC9T:PC 71 BM optimal blend films. 7. Photovoltaic performance Summary of device performance with different treatment (Table S4) Photovoltaic performance of devices based on DRCN5T (Table S5-S8) Photovoltaic performance of devices based on DRCN6T (Table S9-S11) Photovoltaic performance of devices based on DRCN8T (Table S12-S14) Photovoltaic performance of devices based on DRCN9T (Table S15-S17). 8. J sc versus light intensity (P). Figure S6. Measured J sc plotted against light intensity on the logarithmic scale. 9. Mobility measurement. Figure S7. The mobility obtained by space-charge-limited current. S2

3 10. NMR and MS spectra of DRCN4/5/6/8/9T. 11. References. S3

4 1. Materials and measurements. The 1 H and 13 C NMR spectra were recorded on a Bruker AV400 or 600 Spectrometer. High resolution MALDI spectra were collected with a Fourier transform-ion cyclotron resonance mass spectrometer instrument (Varian 7.0TFTICR-MS). Matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) were performed on a Bruker Autoflex III LRF200-CID instrument. The thermogravimetric analysis (TGA) was carried out on a NETZSCH STA 409PC instrument under purified nitrogen gas flow with a 10 C min -1 heating rate. UV Vis spectra were obtained with a JASCO V-570 spectrophotometer. Cyclic voltammetry (CV) experiments were performed with a LK98B II Microcomputer-based Electrochemical Analyzer. All CV measurements were carried out at room temperature with a conventional three-electrode configuration employing a glassy carbon electrode as the working electrode, a saturated calomel electrode (SCE) as the reference electrode, and a Pt wire as the counter electrode. Dichloromethane was distilled from calcium hydride under dry nitrogen immediately prior to use. Tetrabutylammonium phosphorus hexafluoride (Bu 4 NPF 6, 0.1 M) in dichloromethane was used as the supporting electrolyte, and the scan rate was 100 mv s -1. Atomic force microscopy (AFM) was performed using Multimode 8 atomic force microscope in tapping mode. The transmission electron microscopy (TEM) investigation was performed on Philips Technical G 2 F20 at 200 kv. The specimen for TEM measurement was prepared by spin casting the blend solution on ITO/PEDOT:PSS substrate, then floating the film on a water surface, and transferring to TEM grids. The GIXD (Grazing incidence Wide-Angle X-ray Scattering) Samples were prepared on PEDOT:PSS-coated Si substrates using the same preparation conditions as for devices. The data were obtained with an area CCD detector of 3072 by 3072 pixels resolution (225 mm by 225 mm). The monochromated energy of the X-ray source was 10 kev. The X-ray wavelength was Å and the incidence angle was In order to investigate the dependence of J ph on the light intensity, the intensity of S4

5 the light was modulated with a series of two neutral density filters wheels of six filters, allowing for up to 18 steps in intensity from 100 to 2.88 mw cm -2. The geometry structure of the oligothiophene derivatives were optimized by using DFT calculations (B3LYP/6-31G*), and the frequency analysis was followed to assure that the optimized structures were stable states. Time-dependent DFT (TD-DFT) calculation for the S 0 S n transitions using the same functional and basis set were then performed based on the optimized structures at ground states. All calculations were carried out using Gaussian Synthesis Synthesis of compound DRCN4T 2,2'-((5Z,5'Z)-5,5'-((3,3'''-dioctyl-[2,2':5',2'':5'',2'''-quaterthiophene]-5,5'''-diyl)b is(methanylylidene))bis(3-(2-ethylhexyl)-4-oxothiazolidine-5,2-diylidene))dimalo nonitrile Synthesis of compound DF4T. A solution of compound 4 (1.01 g, 2.00 mmol) and compound 5 (1.50 g, 5.00 mmol) in dry toluene was degassed twice followed by the addition of Pd(PPh 3 ) 4 (0.23 g, 0.20 mmol) under the protection of argon. After stirring and refluxing for 24 h, the mixture was extracted with CH 2 Cl 2 (40 ml x 3). The organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using dichloromethane and petroleum (1:2) as eluent to afford DF4T as a red solid (1.00 g, 82%). 1 H NMR (400MHz, CDCl 3 ): δ 9.84 (s, 2H), 7.61 (s, 2H), 7.23 (br, 4H), (t, 4H), (m, 4H), (m, 10H), (t, 6H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , 31.87, 30.27, 29.47, 29.44, 29.39, 29.25, 22.69, MS (MALDI-TOF) m/z: calcd for C 34 H 32 O 2 S 4 [M] +, ; found, Anal. Calcd. For C 34 H 32 O 2 S 4 : C, 67.96; H, Found: C, 67.88; H, S5

6 Synthesis of compound DRCN4T. DF4T (0.12 g, 0.20 mmol) and compound 9 (0.55 g, 2.00 mmol) was dissolved in a dry CHCl 3 (50 ml) solution, and then three drops of piperidine was added to the mixture under the protection of argon. After stirring and refluxing for 12 h, the mixture was extracted with CHCl 3 (50 ml x 3), the organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using chloroform and petroleum (1:1)as eluent and then recrystallized from CHCl 3 to afford DRCN4T as black solid (0.15 g, 66%). 1 H NMR (400MHz, CDCl 3 ): δ 7.98 (s, 2H), 7.30 (s, 2H), 7.28 (s, 2H), 7.25(s, 2H), (d, 4H), (t, 4H), (m, 2H), (m, 8H), (m, 32H), (m, 18H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , 56.24, 49.10, 37.84, 31.88, 30.09, 29.62, 29.42, 29.28, 29.09, 27.93, 230, 22.70, 22.52, 14.15, 14.02, MS (MALDI-TOF) m/z: calcd for C 62 H 76 N 6 O 2 S 6 [M] +, ; found, Anal. Calcd. For C 62 H 76 N 6 O 2 S 6 : C, 65.92; H, 6.78; N, Found: C, 66.06; H, 6.56; N, Melting point (DSC): ~179 C Synthesis of compound DRCN5T (2,2'-((5Z,5'Z)-5,5'-((3,3''',3'''',4'-tetraoctyl-[2,2':5',2'':5'',2''':5''',2''''-quinquethi ophene]-5,5''''-diyl)bis(methanylylidene))bis(3-ethyl-4-oxothiazolidine-5,2-diylid ene))dimalononitrile) DF5T (0.46 g, 0.5 mmol) and compound 10 (0.97 g, 5 mmol) was dissolved in a dry CHCl 3 (50 ml) solution under the protection of argon, and then three drops of piperidine was added to the mixture. After stirring and refluxing for 12 h, the mixture was extracted with CHCl 3 (50 ml x 3), the organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was S6

7 purified by silica gel using chloroform as eluent and recrystallized from CHCl 3 to afford DRCN5T as black solid (0.46 g, 73%). 1 H NMR (400MHz, CDCl 3 ): δ 7.98 (s, 2H), 7.29 (s, 2H), 7.20 (s, 2H), 7.17 (s, 2H), (m, 4H), (t, 8H), (m, 8H), (m, 48H), (m, 12H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , 40.65, 31.89, 31.86, 30.69, 30.18, 29.71, 29.53, 29.47, 29.38, 29.35, 29.26, 22.68, 14.22, MS (MALDI-TOF) m/z: calcd for C 70 H 86 N 6 O 2 S 7 [M] +, ; found, Anal. Calcd. For C 70 H 86 N 6 O 2 S 7 : C, 66.31; H, 6.84; N, Found: C, 66.04; H, 6.55; N, Melting point (DSC): ~217 C Synthesis of compound DRCN6T 2,2'-((5Z,5'Z)-5,5'-((3,3'''',3''''',4'-tetraoctyl-[2,2':5',2'':5'',2''':5''',2'''':5'''',2'''''-s exithiophene]-5,5'''''-diyl)bis(methanylylidene))bis(3-ethyl-4-oxothiazolidine-5,2- diylidene))dimalononitrile Synthesis of compound 2. A solution of 2-(3-octylthienyl)magnesium bromide prepared from 2-bromo-3-octylthienyl (3.50 g, mmol) was added dropwise into a mixture of compound 1 (1.59g, 4.90 mmol) and Ni(dppp) 2 Cl 2 (0.16 g, 0.29 mmol) in diethyl ether (40 ml) under the protection of argon. After stirring and refluxing for 24 h, the solution was cooled to room temperature and quenched with ice water (20 ml). The mixture was extracted with CH 2 Cl 2 (50 ml x 3), the organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using petroleum ether as eluent to afford compound S7

8 2 as yellow liquid (1.92 g, 71%). 1 H NMR (400MHz, CDCl 3 ): δ 7.18 (d, 2H), 7.13 (d, 2H), 7.01 (d, 2H), 6.94 (d, 2H), (t, 4H), (m, 4H), (m, 16H), (t, 6H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , 32.02, 30.78, 29.67, 29.56, 29.41, 22.82, MS (MALDI-TOF) m/z: calcd for C 32 H 42 S 4 [M] +, ; found, Synthesis of compound 3. Under the protection of argon, n-butyllithium (2.0 M, 5 ml, 10 mmol) was dropwise added to the compound 2 (2.22 g, 4 mmol) in dry THF (20 ml) at -78 o C over 0.5 h. After stirring for 0.5 h, the mixture was warmed to room temperature and stirring for 0.5 h. Then Bu 3 SnCl (3.26 g, 10 mmol) was added into the mixture at -78 o C over 0.5 h, the mixture was warmed to room temperature and stirred for 12 h. Subsequently, the mixture was poured into ice water and extracted with CH 2 Cl 2 (20 ml x 3). The organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h and concentrated to afford compound 3, which was used for the next step without purification. Synthesis of compound DF6T. A solution of compound 3 (3.60 mmol) and compound 5 (2.40 g, 7.93 mmol) in dry toluene was degassed twice followed by the addition of Pd(PPh 3 ) 4 (0.21 g, 0.18 mmol) under the protection of argon. After stirring and refluxing for 24 h, the mixture was extracted with CH 2 Cl 2 (50 ml x 3). The organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using dichloromethane and petroleum (2:1) as eluent to afford DF6T as a red solid (2.20 g, 61%). 1 H NMR (400MHz, CDCl 3 ): δ 9.82 (s, 2H), 7.58 (s, 2H), 7.17 (d, 2H), 7.13 (s, 2H), 7.09 (s, 2H), (m, 8H), (m, 8H), (m, 32H), (t, 12H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , 31.91, 30.46, 30.27, 29.56, 29.52, 29.42, 29.29, 22.70, MS (MALDI-TOF) m/z: calcd for C 58 H 78 O 2 S 6 [M] +, ; found, Anal. Calcd. S8

9 For C 58 H 78 O 2 S 6 : C, 69.69; H,7.86. Found: C, 69.50; H, Synthesis of compound DRCN6T. DF6T (0.50 g, 0.5 mmol) and compound 10 (0.97 g, 5 mmol) was dissolved in a dry CHCl 3 (50 ml) solution, and then three drops of piperidine was added to the mixture under the protection of argon. After stirring and refluxing for 12 h, the mixture was extracted with CHCl 3 (50 ml x 3), the organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using chloroform as eluent and then recrystallized from CHCl 3 to afford DRCN6T as black solid (0.44 g, 65%). 1 H NMR (400MHz, CDCl 3 ): δ 7.98 (s, 2H), 7.28 (s, 2H), 7.18 (s, 2H), 7.17(d, 2H), 7.12 (d, 2H), (m, 4H), (t, 8H), (m, 8H), (m, 16H), (t, 12H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , 55.49, 40.65, 31.89, 31.87, 30.60, 30.17, 29.66, 29.55, 29.50, 29.42, 29.39, 29.33, 29.28, 22.69, 14.22, MS (MALDI-TOF) m/z: calcd for C 74 H 88 N 6 O 2 S 8 [M] +, ; found, Anal. Calcd. For C 74 H 88 N 6 O 2 S 8 : C, 65.83; H, 6.57; N, Found: C, 65.60; H, 6.60; N, Melting point (DSC): ~233 C Synthesis of compound DRCN8T 2,2'-((5Z,5'Z)-5,5'-((3,3''''',3'''''',3''''''',4',4''-hexaoctyl-[2,2':5',2'':5'',2''':5''',2'''': 5'''',2''''':5''''',2'''''':5'''''',2'''''''-octithiophene]-5,5'''''''-diyl)bis(methanylylidene ))bis(3-ethyl-4-oxothiazolidine-5,2-diylidene))dimalononitrile Synthesis of compound DF8T. S9

10 A solution of compound 3 (2.00 mmol) and compound 6 (2.19 g, 4.40 mmol) in dry toluene was degassed twice followed by the addition of Pd(PPh 3 ) 4 (0.25 g, 0.20 mmol) under the protection of argon. After stirring and refluxing for 24 h, the mixture was extracted with CH 2 Cl 2 (50 ml x 3). The organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by by silica gel using dichloromethane and petroleum (1:1) as eluent to afford DF8T as a red solid (2.40 g, 69%). 1 H NMR (400MHz, CDCl 3 ): δ9.85 (s, 2H), 7.61 (s, 2H), 7.19 (d, 2H), 7.15 (s, 2H), 7.11 (d, 2H), 7.04 (s, 2H), (m, 12H), (m, 12H), (m, 48H), (t, 18H). 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , 31.91, 30.54, 30.50, 30.26, 29.58, 29.44, 29.30, 22.69, MS (MALDI-TOF) m/z: calcd for C 82 H 114 O 2 S 8 [M] +, ; found, Anal. Calcd. For C 82 H 114 O 2 S 8 : C, 70.94; H, Found: C, 71.05; H, Synthesis of compound DRCN8T. Under the protection of argon, DF8T (0.46 g, 0.4 mmol) and compound 10 (0.77 g, 4 mmol) was dissolved in a dry CHCl 3 (50 ml) solution, and then three drops of piperidine was added to the mixture. After stirring and refluxing for 12 h, the mixture was extracted with CHCl 3 (50 ml x 2), the organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using chloroform as eluent and then recrystallized from CHCl 3 to afford DRCN8T as black solid (0.55g, 79%). 1 H NMR (400MHz, CDCl 3 ): δ 7.99 (s, 2H), 7.29 (s, 2H), 7.18 (s, 2H), 7.16(br, 2H), 7.09(br, 2H), 7.04 (s, 2H), (t, 4H), (m, 12H), (m, 12H), (m, 66H), (t, 18H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , , 55.35, 40.60, 31.96, 30.61, 30.10, 29.78, 29.73, 29.65, 29.50, 29.39, 22.75, MS (MALDI-TOF) m/z: calcd for C 98 H 124 N 6 O 2 S 10 [M] +, ; found, Anal. Calcd. For C 98 H 124 N 6 O 2 S 10 : C, 67.70; H, 7.19; N, Found: S10

11 C, 67.95; H, 7.36; N, Melting point (DSC): ~206 C Synthesis of compound DRCN9T. 2,2'-((5Z,5'Z)-5,5'-((3,3''''',3'''''',3''''''',3'''''''',4',4'',4'''-octaoctyl-[2,2':5',2'':5'',2' '':5''',2'''':5'''',2''''':5''''',2'''''':5'''''',2''''''':5''''''',2''''''''-novithiophene]-5,5'''''''' -diyl)bis(methanylylidene))bis(3-ethyl-4-oxothiazolidine-5,2-diylidene))dimalono nitrile Synthesis of compound DF9T. A solution of compound 7 (2.00 mmol) and compound 8 (2.28g, 4.40 mmol) in dry toluene was degassed twice followed by the addition of Pd(PPh 3 ) 4 (0.25 g, 0.20 mmol) under the protection of argon. After stirring and refluxing for 24 h, the mixture was extracted with CH 2 Cl 2 (50 ml x 3). The organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using dichloromethane and petroleum (1:1) as eluent to afford DF9T as a red solid (1.60 g, 47%). 1 H NMR (400MHz, CDCl 3 ): δ9.82 (s, 2H), 7.58 (s, 2H), 7.12 (s, 4H), 7.00 (s, 4H), (m, 16H), (m, 16H), (m, 70H), (t, 24H). 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , 32.02, 30.52, 30.29, 29.82, 29.56, 29.45, 22.80, MS (MALDI-TOF) m/z: calcd for C 102 H 148 O 2 S 9 [M] +, ; found, Anal. Calcd. For C 102 H 148 O 2 S 9 : C, 72.28; H, Found: C, 72.09; H, Synthesis of compound DRCN9T. Under the protection of argon, DF9T (0.34 g, 0.2 mmol) and compound 10 (0.39 g, 2 S11

12 mmol) was dissolved in a dry CHCl 3 (50 ml) solution, and then three drops of piperidine was added to the mixture. After stirring and refluxing for 12 h, the mixture was extracted with CHCl 3 (50 ml x 2), the organic layer was washed with water and dried over anhydrous Na 2 SO 4 for 3 h. After removal of solvent, the crude product was purified by silica gel using chloroform as eluent and then recrystallized from CHCl 3 to afford DRCN8T as a black solid (0.23g, 56%). 1 H NMR (400MHz, CDCl 3 ): δ 7.99 (s, 2H), 7.29 (s, 2H), 7.18 (s, 2H), 7.11(s, 2H), 7.03(s, 2H), 7.00 (s, 2H), (t, 4H), (m, 16H), (m, 16H), (m, 70H), (t, 30H); 13 C NMR(100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , , , , 55.42, 40.63, 31.95, 30.63, 30.15, 29.71, 29.54, 29.50, 29.37, 29.32, 22.73, MS (MALDI-TOF) m/z: calcd for C 118 H 158 N 6 O 2 S 11 [M] +, ; found, Anal. Calcd. For C 118 H 158 N 6 O 2 S 11 : C, 69.29; H, 7.79; N, Found: C, 67.09; H, 7.95; N, Melting point (DSC): ~168 C. 3. The calculation results. S12

13 Figure S1. The optimized geometries for DRCN4T-DRCN9T. DRCN4/6/8T are centrosymmetric and DRCN5/7/9T are axisymmetric. DRCN6T exhibits non-planar structure. Table S1. The calculation results of dipole moment. Molecules µ g (D) µ e (D) Δµ ge (D) J sc (ma cm -2 ) DRCN4T DRCN5T DRCN6T DRCN7T DRCN8T DRCN9T Δµ ge = [(µ gx µ ex ) 2 + (µ gy µ ey ) 2 + (µ gz µ ez ) 2 ] 1/2 S13

14 4. Thermogravimetric and differential scanning calorimetry analysis. Figure S2. a) TGA plot of DRCN4T-DRCN9T with a heating rate of 10 o C min -1 under N 2 atmosphere. b) DSC plot of DRCN4T-DRCN9T with a heating rate of 10 o C min -1 and a cooling rate of 10 o C min -1 under N 2 atmosphere. Table S2. The thermal properties data of DRCN4T-DRCN9T. Molecules DRCN4T DRCN5T DRCN6T DRCN7T DRCN8T DRCN9T T d ( o C) T m ( o C) T c ( o C) H (J g -1 ) S14

15 5. Cyclic voltammograms. Figure S3. Cyclic voltamsmogram of DRCN4T-DRCN9T in dichloromethane with 0.1 M Bu 4 NPF 6 as the supporting electrolyte at a scan speed of 100 mv s -1. Table S3. The electrochemical data and the calculation results of DRCN4T-DRCN9T. molecules Methods DRCN4T DRCN5T DRCN6T DRCN7T DRCN8T DRCN9T HOMO (ev) LUMO (ev) Eg (ev) CV DFT CV DFT CV DFT S15

16 6. Morphology analysis. Figure S4. AFM topography images of optimal blend films cast from chloroform solution: (a) DRCN4T:PC 71 BM, the RMS roughness is 16.2 nm, large domain size (~200 nm) is observed. (b) DRCN5T:PC 71 BM, the RMS roughness is 0.80 nm. (c) DRCN6T:PC 71 BM, the RMS roughness is 0.70 nm. (d) DRCN7T:PC 71 BM, the RMS roughness is 0.39 nm. (e) DRCN8T:PC 71 BM, the RMS roughness is 0.81 nm. (f) DRCN9T:PC 71 BM, the RMS roughness is 0.57 nm. S16

17 7. Photovoltaic performance. Figure S5. The J-V curve of an optimal device based on DRCN5T:PC 71 BM (w:w=1:0.8) certified by National Center of Supervision & Inspection on Solar Photovoltaic Products Quality of China (CPVT). S17

18 7.1. Summary of device performance with different treatment (Table S4). Molecules Treatment V oc (V) J sc (ma cm -2 ) FF PCE (%) DRCN4T NO NO DRCN5T TA(120 o C) TA+SVA NO DRCN6T TA(140 o C) TA+SVA NO DRCN7T TA(90 o C) TA+SVA NO DRCN8T TA(90 o C) TA+SVA NO DRCN9T TA(110 o C) TA+SVA *TA is referred to thermal annealing, the TA time is 10 min; SVA is referred to solvent vapor annealing, the SVA time is 60 s Photovoltaic performance of devices based on DRCN5T. Table S5. Photovoltaic performance of BHJ solar cells based on DRCN5T:PC 71 BM with weight ratios (w:w) of 1:0.5, 1:0.8 and 1:1 cast from CHCl 3 with TA at 120 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Ratio of D:A V oc (V) J sc (ma cm -2 ) FF PCE (%) 1: : : S18

19 Table S6. Photovoltaic performance of BHJ solar cells based on DRCN5T:PC 71 BM with weight ratio at 1:0.8 with thickness of 80 nm, 120 nm, 150 nm cast from CHCl 3 with TA at 120 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Thickness (nm) V oc (V) J sc (ma cm -2 ) FF PCE (%) Table S7. Photovoltaic performance of BHJ solar cells based on DRCN5T:PC 71 BM with weight ratio at 1:0.8 with thickness of 120 nm cast from CHCl 3 with different TA temperature using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Temperature ( o C) V oc (V) J sc (ma cm -2 ) FF PCE (%) NO Table S8. Photovoltaic performance of BHJ solar cells based on DRCN5T:PC 71 BM with weight ratio at 1:0.8 with thickness of 120 nm cast from CHCl 3 with TA at 120 o C for 10 min, and different time for SVA using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. The solvent vapor is CHCl 3. SVA time (s) V oc (V) J sc (ma cm -2 ) FF PCE (%) NO S19

20 7.3. Photovoltaic performance of devices based on DRCN6T. Table S9. Photovoltaic performance of BHJ solar cells based on DRCN6T:PC 71 BM with weight ratios (w:w) of 1:0.5, 1:0.8 and 1:1 cast from CHCl 3 with TA at 140 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Ratio of D:A V oc (V) J sc (ma cm -2 ) FF PCE (%) 1: : : Table S10. Photovoltaic performance of BHJ solar cells based on DRCN6T:PC 71 BM with weight ratio at 1:0.8 with thickness of 80 nm, 120 nm, 150 nm cast from CHCl 3 with TA at 140 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Thickness (nm) V oc (V) J sc (ma cm -2 ) FF PCE (%) Table S11. Photovoltaic performance of BHJ solar cells based on DRCN6T:PC 71 BM with weight ratio at 1:0.8 with thickness of 120 nm cast from CHCl 3 with different TA temperature using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Temperature ( o C) V oc (V) J sc (ma cm -2 ) FF PCE (%) NO S20

21 7.4. Photovoltaic performance of devices based on DRCN8T. Table S12. Photovoltaic performance of BHJ solar cells based on DRCN8T:PC 71 BM with weight ratios (w:w) of 1:0.5, 1:0.8 and 1:1 cast from CHCl 3 with TA at 90 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Ratio of D:A V oc (V) J sc (ma cm -2 ) FF PCE (%) 1: : : Table S13. Photovoltaic performance of BHJ solar cells based on DRCN8T:PC 71 BM with weight ratio at 1:0.8 with thickness of 80 nm, 120 nm, 150 nm cast from CHCl 3 with TA at 90 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Thickness (nm) V oc (V) J sc (ma cm -2 ) FF PCE (%) Table S14. Photovoltaic performance of BHJ solar cells based on DRCN8T:PC 71 BM with weight ratio at 1:0.8 with thickness of 120 nm cast from CHCl 3 with different TA temperature using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Temperature ( o C) V oc (V) J sc (ma cm -2 ) FF PCE (%) NO S21

22 7.5. Photovoltaic performance of devices based on DRCN9T. Table S15. Photovoltaic performance of BHJ solar cells based on DRCN9T:PC 71 BM with weight ratios (w:w) of 1:0.5, 1:0.8 and 1:1 cast from CHCl 3 with TA at 110 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Ratio of D:A V oc (V) J sc (ma cm -2 ) FF PCE (%) 1: : : Table S16. Photovoltaic performance of BHJ solar cells based on DRCN6T:PC 71 BM with weight ratio at 1:0.8 with thickness of 80 nm, 120 nm, 150 nm cast from CHCl 3 with TA at 140 o C for 10 min using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Thickness (nm) V oc (V) J sc (ma cm -2 ) FF PCE (%) Table S17. Photovoltaic performance of BHJ solar cells based on DRCN9T:PC 71 BM with weight ratio at 1:0.8 with thickness of 120 nm cast from CHCl 3 with different TA temperature using PFN/Al as the cathode under illumination of AM 1.5 G, 100 mw cm -2. Temperature ( o C) V oc (V) J sc (ma cm -2 ) FF PCE (%) NO S22

23 8. J sc versus light intensity (P). Figure S6. Measured J sc of DRCN5T-DRCN9T:PC 71 BM solar cells plotted against light intensity on the logarithmic scale. The fitted power law yield α for DRCN5-DRCN9T:PC 71 BM are 0.964±0.006, 0.918±0.008, 0.956±0.005, 0.954±0.007 and ±0.008, respectively. At short circuit, the bimolecular recombination should be minimum (α 1) for maximum carrier sweeping out. Any deviation from α 1 implies bimolecular recombination Mobility measurement. Figure S7. Experimental dark-current densities for a) DRCN5T:PC 71 BM, b) DRCN6T:PC 71 BM, c) DRCN8T:PC 71 BM and d) DRCN9T:PC 71 BM optimal hole-only devices. The solid lines represent the fit using a model of single carrier SCLC with field-independent mobility. The J D -V characteristics are corrected for the built-in voltage V bi that arises from the work function difference between the contacts. (a) cm 2 V -1 s -1, (b) cm 2 V -1 s -1, (c) cm 2 V -1 s -1, (d) cm 2 V -1 s -1. S23

24 10. NMR and MS spectra of DRCN4-DRCN9T. Figure S8. 1 H NMR and 13 C NMR spectra of DRCN4T at 300K in CDCl 3 S24

25 Figure S9. 1 H NMR and 13 C NMR spectra of DRCN5T at 300K in CDCl 3. S25

26 Figure S10. 1 H NMR and 13 C NMR spectra of DRCN6T at 300K in CDCl 3. S26

27 Figure S11. 1 H NMR and 13 C NMR spectra of DRCN8T at 300K in CDCl 3. S27

28 Figure S12. 1 H NMR and 13 C NMR spectra of DRCN9T at 300K in CDCl 3. S28

29 Figure S13. MS (MALDI-TOF) spectra of DRCN4T. S29

30 Figure S14. MS (MALDI-TOF) spectra of DRCN5T. S30

31 Figure S15. MS (MALDI-TOF) spectra of DRCN6T. S31

32 Figure S16. MS (MALDI-TOF) spectra of DRCN8T. S32

33 Figure S17. MS (MALDI-TOF) spectra of DRCN9T. S33

34 11. References. 1. Gaussian 09, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, Lenes, M.; Morana, M.; Brabec, C. J.; Blom, P. W. M. Adv. Funct. Mater. 2009, 19, S34