SUPPORTING INFORMATION Conjugated Organic Cations to Improve the Optoelectronic Properties of 2D/3D Perovskites Jesús Rodríguez-Romero, Bruno Clasen Hames, Iván Mora-Seró and Eva M. Barea* Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain Email: sero@uji.es, barea@uji.es Experimental Methods: Device fabrication: Fluorine doped tin oxide (FTO) substrates were partially treated with Zn and HCl 2M and further cleaned with soap (Hellmanex) and deionized water, followed by sonication in a) ethanol and b) i-proh during 15 min for each step, and dried with compressed air. Then, the resultant substrates were exposed to UV-O 3 during 10 min. A compact layer of TiO 2 was deposited on the substrates by spray pyrolisis process of titanium diisopropoxide bis(acac) solution (75% in 2-propanol, Sigma-Aldrich) diluted with absolute ethanol in 1:9 v/v proportion, respectively. The mesoporous TiO 2 layer was deposited through spin-coating method of a suspension prepared from DYESOL-30NRD paste, diluted with absolute ethanol. After drying at 100 C during 10 min the substrates were gradually heated to 500 ºC and cooled to room temperature. The perovskite absorber layers were deposited through spin coating process of 0.225 M precursor solution at 5000 rpm for 20 s. The perovskite precursor solutions were prepared by addition of corresponding quantities of PbI 2, anilinium iodide (AnyI) or butylammonium iodide (BAI) and methylammonium iodide (MAI) in a mixture of DMF and DMSO (see Tables S1 and S2). We use a modified methodology of the successful hot casting process. 1 The perovskite precursor solution was heated to 70 C during all the process. On the other hand, the substrates with a compact/mesoporous layer of TiO 2 were heated to 130 C during 30 min before to start the deposition of the perovskite layer and they were maintained heating until the process was concluded. Once the perovskite was deposited by spin-coating process (50 µl; 5000 rpm without acceleration; 20 s), the respective substrates were heated 10 min
more at 100 C. The substrates should show from a yellow to a green-brown layer, depending on its dimensionality. After the substrates were cooled to room temperature the hole transporting layer (HTL) was deposited by spin coating at 4000 rpm during 30 s. The HTM was prepared dissolving 72.3 mg of (2,2,7,7 -tetrakis(n,n-di-pmethoxyphenylamine)-9,9-spirobifluorene)(spiro-ometad), 28.8 µl of 4-tertbutylpyridine, and 17.5 µl of a stock solution of 520 mg/ml lithium bis- (trifluoromethylsulfonyl)imide in acetonitrile in 1 ml of chlorobenzene. Finally, 60 nm of gold was thermally evaporated in the vacuum chamber on top of the device to form the electrode contacts. The complete device fabrication was carried outside the globe box. Table S1 Amount of each precursor for preparing the corresponding thin films for the AnyI family. n Molar relation PbI 2 :PhAI:MAI *PbI 2 (gr) AnyI (gr) MAI (gr) DMF DMSO 1 1:2:0 0.1136 0.1089 0 1 0.095 2 2:2:1 0.1136 0.0544 0.0195 1 0.095 3 3:2:2 0.1136 0.0363 0.0261 1 0.095 4 4:2:3 0.1136 0.0272 0.0294 1 0.095 5 5:2:4 0.1136 0.0218 0.0313 1 0.095 *0.225 M Pb 2+ Table S2 Amount of each precursor for preparing the corresponding thin films for the BAI family. n Molar relation PbI 2 :BAI:MAI *PbI 2 (gr) BAI (gr) MAI (gr) DMF DMSO 1 1:2:0 0.1136 0.0990 0 1 0.095 2 2:2:1 0.1136 0.0495 0.0195 1 0.095 3 3:2:2 0.1136 0.0330 0.0261 1 0.095 4 4:2:3 0.1136 0.0248 0.0294 1 0.095 5 5:2:4 0.1136 0.0198 0.0313 1 0.095 *0.225 M Pb 2+ Device characterization: Photovoltaic devices were characterized using a Sun 2000 system solar simulator from Abet technologies. The light intensity was adjusted to 100 mwcm -2 using a calibrated Si solar cell. Devices were measured using two masks to define an active area of 0.101 and 0.12 cm 2. UV-Vis spectroscopy was evaluated using a Varian Cary 300 Bio spectrophotometer. The XRD pattern of the prepared solids were measured using X-ray diffractometer (D8 Advance, Bruker-AXS) ( Cu Kα, wavelength λ=1.5406 Å). The EL of the devices were performed by using a potentiostat (Gamry Reference 3000) to
apply a constant voltage, synchronized with an Andor-iDus DV-420A intensified CCD with thermoelectric cooling coupled with a Newport 77400 MS125TM spectrograph to acquire the output light. Table S3. Photovoltaic performances of AnyIPb n solar cells obtained from the reverse scan of the J-V curves. Table S4. Photovoltaic performances of BAIPb n solar cells obtained from the reverse scan of the J-V curves.
Figure S1. XRD of (C 6 H 5 NH 3 I) 2 (CH 3 NH 3 I) n-1 (PbI 2 ) n (n= 5) with and without annealing, see Experimental Methods. Figure S2: Electroluminescence obtained from devices prepared with both AnyIPb n and BAIPb n with n=3 at different applied bias.
Figure S3. Absorbance and picture of 2D/3D HPVK with different n a) AnylPb n and b) BAIPb n. Acknowledgment. This study was supported by the University Jaume I (project UJI- B2016-35), by MINECO of Spain (project MAT2016-76892-C3-1-R), and by Generalitat Valenciana (Project PROMETEOII/2014/020). J.R.R. thanks CONACyT-México for a postdoctoral fellowship. B.C.H is grateful for support of the National Council of Technological and Scientific Development (CNPq), Brazil, through the Science without Borders program. Reference 1. Tsai, H.; Nie, W.; Blancon, J.-C.; Stoumpos, C. C.; Asadpour, R.; Harutyunyan, B.; Neukirch, A. J.; Verduzco, R.; Crochet, J. J.; Tretiak, S.; Pedesseau, L.; Even, J.; Alam, M. A.; Gupta, G.; Lou, J.; Ajayan, P. M.; Bedzyk, M. J.; Kanatzidis, M. G.; Mohite, A. D., High-efficiency two-dimensional Ruddlesden Popper perovskite solar cells. Nature 2016, 536, 312-316.