Supporting Information Functional p-type, polymerized organic electrode interlayer in CH 3 NH 3 PbI 3 perovskite/fullerene planar heterojunction hybrid solar cells Tsung-Yu Chiang 1, Gang-Lun Fan 5, Jun-Yuan Jeng 1, Kuo-Cheng Chen 1, Peter Chen 1, 2, 3, Ten-Chin Wen 4, Tzung-Fang Guo 1, 2,3, *, and Ken-Tsung Wong 5, 6, * 1 Department of Photonics, National Cheng Kung University, Tainan, Taiwan 701 2 Advanced Optoelectronic Technology Center (AOTC) National Cheng Kung University, Tainan, Taiwan 701 3 Research Center for Energy Technology and Strategy (RCETS) National Cheng Kung University, Tainan, Taiwan 701 4 Department of Chemical Engineering National Cheng Kung University, Tainan, Taiwan 701 5 Department of Chemistry National Taiwan University, Taipei, Taiwan 106 6 Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan 106 AUTHOR INFORMATION Corresponding Author *guotf@mail.ncku.edu.tw Corresponding Author *kenwong@ntu.edu.tw S-1
Fig. S1. (a) The testing results about the solvent-resisting property of polymerized VB- DAAF film on glass/ito/pedot:pss substrate. The polymerized VB-DAAF film was washed by the solvent (a mixture of γ-butyrolactone (GBL):dimethyl sulfoxide (DMSO) (7:3, v/v)). The measurement of UV-Vis spectra indicates that the polymerized VB-DAAF film is still on glass/ito/pedot:pss substrate after the solvent washing. (b) The testing results about the solvent-resisting property of polymerized VB-DAAF film on PEI/ITO substrate by a UV-assisted process. The polymerized VB-DAAF film is still on PET/ITO substrate after the solvent washing. S-2
Fig. S2. The J-V curves of dark current measurement for CH 3 NH 3 PbI 3 perovskite solar cells fabricated on ( ) galss/ito/pedot:pss and ( ) glass/ito/polymerized VB- DAAF substrates. S-3
Fig. S3. GAXRD measurement of CH 3 NH 3 PbI 3 perovskite film on glass/ito/polymerized VB-DAAF substrate. S-4
Fig. S4. The J-V curves for CH 3 NH 3 PbI 3 perovskite/c 60 hybrid solar cells fabricated on the glass/ito/polymerized VB-DAAF ( ) at 1.0 %, 2000 rpm, ( ) at 1.0 %, 4000 rpm, ( ) at 1.0 %, 7000 rpm, and ( ) at 0.3 %, 7000 rpm. Table S1. The photovoltaic parameters of CH 3 NH 3 PbI 3 perovskite/c 60 hybrid solar cells (Fig. S4) fabricated with the varied thickness of polymerized VB-DAAF films by changing the spinning speed. Device structure V oc [V] J sc [ma/cm 2 ] FF PCE [%] R s [Ω cm 2 ] Glass/ITO/polymerized VB-DAAF (2000 rpm, 1.0 %)/CH 3 NH 3 PbI 3 /C 60 /BCP/Al Glass/ITO/polymerized VB-DAAF (4000 rpm, 1.0 %)/CH 3 NH 3 PbI 3 /C 60 /BCP/Al Glass/ITO/polymerized VB-DAAF (7000 rpm, 1.0 %)/CH 3 NH 3 PbI 3 /C 60 /BCP/Al Glass/ITO/polymerized VB-DAAF (7000 rpm, 0.3 %)/CH 3 NH 3 PbI 3 /C 60 /BCP/Al 0.97 19.43 0.57 10.71 28.72 0.99 18.72 0.65 12.16 14.93 0.99 18.96 0.73 13.79 9.05 1.02 18.92 0.78 15.17 4.46 S-5
Fig. S5. The transmittance spectra of ( ) glass/ito, ( ) PET/ITO, and ( ) PET (PET/ITO after etching the ITO layer) substrates. S-6
Fig. S6. The box chart of photovoltaic parameters for hybrid solar cells of glass/ito/pedot:pss/ch 3 NH 3 PbI 3 perovskite/c 60 /BCP/Al and glass/ito/polymerized VB-DAAF/CH 3 NH 3 PbI 3 perovskite/c 60 /BCP/Al configurations. S-7
Fig. S7. Scheme to synthesize VB-DAAF monomer. S-8
Fig. S8. 1 H NMR spectra of VB-F. Preparation of VB-F: To a two-necked flask was added 2,7-dibromo-9,9-bis(4- hydroxyphenyl)fluorene 1 (7.62 g, 15.0 mmol), potassium carbonate (8.29 g, 60.0 mmol), and DMSO (50 ml). The mixture was stirred at room temperature under N 2 for 30 minutes, followed by adding 4-vinylbenzyl chloride (5.04 g, 33.0 mmol). The resulting reaction mixture was heated and stirred at 60 o C for 2 h stirring. After cooling to room temperature, the solution was poured into water, and the precipitate was filtered to give the crude product. The crude product was dissolved in CH2Cl2 and then extracted with water and brine. The combined organic extracts were dried over MgSO4 and concentrated. After removal of the solvent, the resulting residue was purified through re-precipitation from CH 2 Cl 2 and methanol to afford VB-F (11.04 g, 99%) as a white solid. 1 H NMR (DMSO-d 6, 400 MHz): δ 7.92 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 8.0 Hz, 2H), 7.53 (s, 2H), 7.48 (d, J = 8.0 Hz, 4H), 7.39 (d, J = 8.0 Hz, 4H), 7.02 (d, J = 8.8 Hz, 4H), 6.92 (d, J = 8.8 Hz, 4H), 6.73 (dd, J 1 = 10.8 Hz, J 2 = 17.6 Hz, 2H), 5.83 (d, J = 17.6 Hz, 2H), 5.26 (d, J = 10.8 Hz, 2H), 5.03 (s, 4H) ppm. S-9
Fig. S9. 13 C NMR spectra of VB-F. 13 C NMR (CDCl 3, 100 MHz): δ 157.7, 153.4, 137.7, 137.2, 136.6, 136.3, 136.2, 130.6, 129.1, 128.9, 127.5, 126.3, 121.7, 121.4, 114.6, 114.0, 69.8, 64.4 ppm. HRMS (m/z, FAB+) calcd. for C 43 H 79 32 Br 79 BrO 2 738.0769, found 738.0770; calcd. for C 43 H 79 32 Br 81 BrO 2 740.0749, found 740.0748; calcd. for C 43 H 81 32 Br 81 BrO 2 742.0728, found 742.0721. S-10
Fig. S10. 1 H NMR spectra of VB-DAAF. Preparation of VB-DAAF: To a two-necked flask was added VB-F (7.41 g, 10.0 mmol), di-p-methoxyphenylamine 2 (5.04 g, 22.0 mmol), palladium acetate (112 mg, 0.5 mmol), sodium tert-butoxide (3.84 g, 5.6 mmol), toluene (150 ml), and tri-tertbutyl phosphine (20 ml, 1.0 mmol, 0.05 M in toluene). The reaction mixture was stirred and heated at 75 o C under argon for 12 h. After cooling to room temperature, the solution was quenched and filtered by Celite and washed with CH 2 Cl 2. The filtrate was extracted with CH 2 Cl 2 and water. The combined organic extracts were dried over MgSO 4 and concentrated. The residue was purified by column chromatography, and the resulting product was purified through re-precipitation from CH 2 Cl 2 and methanol to afford VB-DAAF (8.18 g, 79%) as a light yellow solid. 1 H NMR (DMSO-d 6, 400 MHz): δ 7.52 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 4H), 7.40 (d, J = 8.4 Hz, 4H), 6.95-6.92 (m, 8H), 6.89-6.82 (m, 16H), 6.78-6.70 (m, 6H), 5.84 (d, J = 17.6 Hz, 2H), 5.26 (d, J = 11.2 Hz, 2H), 5.02 (s, 4H), 3.71 (s, 12H). S-11
Fig. S11. 13 C NMR spectra of VB-DAAF. 13 C NMR (DMSO-d 6, 100 MHz): δ 157.0, 155.4, 151.9, 147.0, 140.3, 137.6, 136.7, 136.3, 132.2, 128.6, 128.0, 126.2, 126.0, 120.0, 119.5, 117.7, 114.8, 114.4, 68.9, 63.1, 55.2. HRMS (m/z, FAB+) calcd. for C 71 H 60 N 2 O 6 1036.4451, found 1036.4435. S-12
Fig. S12. The differential scanning calorimetry (DSC) analysis of VB-DAAF. ( ) The first DSC scan of pristine VB-DAAF exhibited a glass transition temperature (T g ) of ca. 91 o C. In addition, the broad exothermic peak at ca. 144 o C corresponds to the thermal polymerization of VB-DAAF, and the exothermic peak around 200 o C may be attributed to additional polymerization of the residue styryl groups. In contrast, ( ) the second scan features no apparent signals that can be detected up to 275 o C, implying the existence of a high degree of polymerization between the styryl groups. VB- DAAF first scan VB- DAAF second scan Heat flow (a.u., Exo up) 1 st scan 2 nd scan 91.0 144.1 201.1 50 100 150 200 250 Temperature ( o C ) S-13
Fig. S13. (a) UPS (He I) for the surface measurement of glass/ito/polymerized VB- DAAF sample. Inset: the onset (E i ) and cutoff (E cut-off ) energy regions for the UPS measurement. (b) UV-Vis spectrum of polymerized VB-DAAF film on quartz substrate. HOMO: 21.21 - (20.94-4.91)= 5.18 (ev) LUMO: 1240/418 = 2.97 (ev), 5.18-2.97 = 2.21 (ev) S-14