SUPPORTING INFORMATION

Transcription

1 Current Density (ma/cm 2 ) Current Density (ma/cm 2 ) SUPPORTING INFORMATION New Electron Acceptor Derived from Fluorene: Synthesis and its Photovoltaic Properties P. Nagarjuna, Anirban Bagui, Jianhui Hou, Surya Prakash Singh Light J-V characteristics of PBDTTT-C-T:N3/N6 solar cells: 2 PBDTTT-C-T:N3 OSC w/o DIO 2 PBDTTT-C-T:N3 OSC (D/A ratio 1:2) :1 (D:A) 1:2 (D:A) 1:3 (D:A) Voltage(V) (a) Voltage(V) (b) 1% DIO 3% DIO 5% DIO 2 PBDTTT-C-T:N6 OSC w/o DIO 2 PBDTTT-C-T:N6 OSC (D/A ratio 1:1) Current Density (ma/cm 2 ) -2 1:1 (D:A) 1:2 (D:A) 1:3 (D:A) Voltage(V) (c) Current Density (ma/cm 2 ) % DIO 3% DIO 5% DIO Voltage(V) (d) Figure S1: Light J-V curves of the polymer photovoltaic devices made from PBDTTT-C- T:N3 blends (a) with different donor-acceptor ratio (w/o DIO), (b) with different DIO content at fixed D/A ratio of 1:2 and the solar cells made from PBDTTT-C-T:N6 blends (c) with different donor-acceptor ratio (w/o DIO), (d) with different DIO content at fixed D/A ratio of 1:1. S1

2 Current density (ma/cm 2 ) Current (ma) 2.x1-5 Ferrocene in O-DCB 1.x x x x Potential (V) Figure S2: Cyclic voltammetry of standard reference ferrocene in 1,2-dichloro benzene. Table S1: Absorption coefficient values for N3 and N6 with PCBM Acceptor λ max (nm) Absorption coefficient (M -1 cm -1 ) PC 61 BM N N PTB7:PC 7 BM (2:3) -5-1 PCE = 6.2% V oc =.7 V = 15.4 ma/cm2 J sc FF = 58% Applied voltage (volt) Figure S3: Characteristic current density vs. voltage (J-V) curve of inverted structure solar cells with device configuration of ITO/ZnO/PTB7:PC 61 BM/MoO 3 /Ag. S2

3 IPCE (%) 7 PTB7:PC 61 BM Wavelenth (nm) Figure S4: The external quantum efficiency (EQE) curves of the corresponding PTB7:PC 61 BM based device. 1). Synthesis of fullerene acceptors and characterization by 1 H-NMR, 13 C-NMR (Hz), ESI-MS, MALDI-TOF. A) Synthesis of N3 A1). Methyl 4-(9,9-didecyl-9H-fluorene-2-carbonyl) benzoate:- Terephthalic acid Methyl mono methyl ester chloride (8.5 mg,.4 mmol) was dissolved in CH 2 Cl 2 (4mL). Aluminiumtrichloride (12 mg,.89 mmol) was added in portions at C. Subsequently, 9,9- didecyl-9h-fluorene (2 mg,.49 mmol) in CH 2 Cl 2 (4 ml) was added. The reaction was allowed to stir until the clear solution (± 45 min.). Subsequently, the reaction mixture was stirred for another 2 min. at 4 C, the reaction mixture turned to reddish brown, Cooling to room temperature was followed by removal of the solvent. The product was purified by column chromatography (silica gel; ethyl acetate: hexane, 3%) yielded (6%) pure product. 1 H-NMR(ppm)CDCl 3,5(MHz): (d, 2H), (m, 3H), (m, 3H), (m, 3H), (s, 3H), (m, 4H), (m, 32H), (t, 6H), (solvent peaks). 13 CNMR(Hz)CDCl 3,1(MHz): ,179.6,151.87,15.99,146.4,139.64,135.26,128.31,127.64,126.9,122.94,122.17,12.6,119.36,55.21,4.8,37.42,33.17,31.77,29.85,29.43,29.16,23.67,22.56,19.17,14.1. S3

4 FTIR(cm 1 )KBr: , , , ,166.57,165.57, , , , , , ,118.39, ESI-MS (m/z):- 61(15%) A2).Methyl4-(9,9-didecyl-9H-fluorene-2yl(2tosylhydrazono)methyl)benzoate :- Methyl4- (9,9-didecyl-9H-fluorene-2-carbonyl-)benzoate(4mg,.659mmol)and p-toluene sulfonyl hydrazide(368 mg, mmol) were dissolved in methanol (1 ml). The resulting mixture was heated under reflux condition and reaction was monitored by TLC (silica gel, ethyl acetate). After 5h the conversion almost completed, cooling to room temperature the solvent was evaporated in vacuo. Purification was enforced by column chromatography (silica gel; EA: Hexane, 3%) yielded 36 mg (7%) of the title compound. 1 H-NMR(ppm)CDCl 3,3(MHz): (d, 2H, J=8.39), (d, 2H, J=8.39), (d,1h, J=7.554), (d, 2H), (m, 7H), (d,1h, J=7.554), (s, 3H), (s,3h), (m, 4H), (m, 32H), (t, 6H). 13 C-NMR(Hz)CDCl 3,3(MHz): , 15.99, , , 14.92, ,135.51, 13.97, 13.85, , , , , , , , , , , 123.5, 12.99, 12.32, 52.25, 4.8, 31.88, 29.99, 29.58, 29.52, 29.26, 24.3, 23.78, 22.71, 21.67, FT-IR (cm -1 ) KBr: , , , , , , , , , , , , , ESI-MS (m/z):- 777 (1%) B) Synthesis of N6:- B1).Synthesis of the 9,9-didecyl-9H-fluoren-2-yl-C 61 -butyric acid (F 1 CBA) :- 9,9- didecyl-9h-fluoren-2-yl-c61-butyric acid methyl ester 8mg was dissolved in 1ml of chlorobenzene, and to this solution(7ml) of acetic acid and concentrated was added the mixture was heated to reflux for overnight. The solvent remove was remove in vacuo and pure acid compound was collected through column chromatography by elute hexane and ehtylacetate at 1:1 ratio, yielded 5mg (7%). 1 H-NMR (ppm)cdcl 3,3(MHz): (m,4h), (m 3H,) (bs, 2H), (t, 2H), (m, 6H), (m, 32H),.86 (s, 6H) (solvent peak). S4

5 MALDI-TOF (m/z) : (1%). A1) 1 H-NMR A1) 13 C-NMR S5

6 A2) 1 H-NMR A2) 13 C-NMR S6

7 B1) 1 H-NMR 1 H-NMR- N3 S7

8 1 H-NMR N6 References (1) Singh, S. P.; Pavan. K. CH.; Sharma, G. D.; Kurchania, R.; Roy, S. M. Synthesis of a Modified PC7BM and Its Application as an Electron Acceptor with Poly(3- hexylthiophene) as an Electron Donor for Efficient Bulk Heterojunction Solar Cells. Adv. Funct. Mater. 212, 22, (2) Singh, S. P.; Pavan, K. CH.; Nagarjuna, P.; Sharma, G. D.; Biswas, S.; Mikroyannidis, J. A. Diarylmethanofullerene: Efficient Polymer Solar Cells with Low-Band-Gap Copolymer. J. Phys. Chem. C. 213, 117, (3) Sukeguchi, D.; Singh, S. P.; Mamidi R. R.; Yoshiyama, H.; Afre, A. R.; Hayashi, Y.; Inukai, H.; Soga, T.; Nakamura, S.; Shibata, N. et al. New Diarylmethanofullerene Derivatives and Their Properties for Organic Thin-Film Solar Cells. Beilstein Journal of Organic Chemistry. 29, 5, 7. S8