# Fileset

[SI file.pdf](https://mdr.nims.go.jp/filesets/a09a2ce0-c1ee-4c45-8121-c6e4afa40391/download)

## Creator

[Dhruba B. Khadka](https://orcid.org/0000-0001-9134-3890), [Yasuhiro Shirai](https://orcid.org/0000-0003-2164-5468), [Ryoji Sahara](https://orcid.org/0000-0003-0788-2985), [Masatoshi Yanagida](https://orcid.org/0000-0002-8065-7875), Kenjiro Miyano

## Rights

This is the peer reviewed version of the following article: D. B. Khadka, Y. Shirai, R. Sahara, M. Yanagida, K. Miyano, Ameliorating Defects in Wide Bandgap Tin Perovskite Solar Cells Using Fluorinated Solvent and Hydrazide. Small 2024, 2410048, which has been published in final form at https://doi.org/10.1002/smll.202410048. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Ameliorating Defects in Wide Bandgap Tin Perovskite Solar Cells Using Fluorinated Solvent and Hydrazide](https://mdr.nims.go.jp/datasets/239b5611-3e32-4152-943f-a16832bb238a)

## Fulltext

S-1  Supporting Information Ameliorating Defects in Wide Bandgap Tin Perovskite Solar Cells Using Fluorinated Solvent and Hydrazide    Dhruba B. Khadka1*, Yasuhiro Shirai1, Ryoji Sahara2, Masatoshi Yanagida1, and Kenjiro Miyano1   1Photovoltaic Materials Group, Center for GREEN Research on Energy and Environmental Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan  2Computational Structural Materials Group, Research Center for Structural Materials, National Institute for Materials Science (NIMS), 1-2-1, Sengen, Tsukuba, Ibaraki 305-0047, Japan Corresponding Author *E-mail: KHADKA.B.Dhruba@nims.go.jp          mailto:KHADKA.B.Dhruba@nims.go.jpS-2   Table and Figures   Figure S1. SEM images of WB-Sn-HP films with surface treatment using different F-BHZ precursor concentrations; a) control, b) 0.5 mg/ml, c) 1 mg/ml, d) 1.5 mg/ml, and e) 2 mg/ml, respectively.     S-3     Figure S2. XRD patterns of WB-Sn-HP films [ 0 mg/ml (control), 0.5 mg/ml (ST-1), 1 mg/ml (ST-2), 1.5 mg/ml (ST-3), and 2 mg/ml (ST-4)]. a) XRD patterns zoomed-in 2𝜃<10o). b) XRD patterns of full 2𝜃 range. c) Normalized XRD patterns zoomed in dominant peaks (100) and (200).    Figure S3. FWHM of WB-Sn-HP films; (a) control, (b) ST-2 (1 mg/ml), and (c) ST-4 (2mg/ml).  S-4   Figure S4. a) PL spectra of WB-Sn-HP films with F-BHZ treatment (0-2 mg; control, ST-1 (0.5 mg/ml), ST-2 (1 mg/ml), ST-3 (1.5 mg/ml), ST-4 (2 mg/ml) on ITO substrates (ITO/Sn-HP). b) Normalized PL spectra.   Table S1. Summarized device parameters of the WB-Sn-PSCs (control and ST devices). The tabulated data present the best device parameters, the average value, and the standard deviation (SD) (20 devices from 4 batches).    F-BHZ (mg/ml) JSC (mA cm-2) VOC (V) FF PCE (%) PCE (average ± SD) 0 12.58 0.914 0.692 7.96 7.09 ± 0.41 12.76 0.928 0.622 7.37 0.5 14.12 0.958 0.722 9.77 8.48 ± 0.56 14.24 0.946 0.662 8.92 1 14.37 1.024 0.757 11.14 10.58 ± 0.39 14.465 1.036 0.696 10.43 1.5 13.78 1.014 0.736 10.28 9.62 ± 0.36 14.465 0.994 0.684 9.84 2 12.83 0.956 0.714 8.75 8.22 ± 0.37 13.37 0.976 0.676 8.82 S-5       Figure S5. Statistics of device parameters for the WB-Sn-PSCs with control and ST (0.5-2 mg/ml; F-BHZ) films. Histogram of device parameters: (a) JSC, (b) VOC, (c) FF, and (d) PCE of 20-PSC devices fabricated in 4 different batches.         S-6      Figure S6. (a) absorption spectra and (b) absorption spectra zoom at the band gap edge of the control and F-BHZ-treated wide bandgap tin perovskite films. The encircled regions highlight the change in absorption spectra.     Figure S7. Bandgap energy of WB-Sn-HP; (a) control and (b) ST calculated from the EQE spectra analysis. S-7     Table S2. Summary of device reports on WB-Sn-perovskite (mixed cations/anions, functional additives, passivation, and interfacial layer).      Device structure WB-Sn-HP Method Eg (eV) JSC (mAcm-2) VOC (V) FF PCE (%) date Ref. FTO/TiO2/MASnBr3/P3HT/Ag MASnBr3 Co-evaporation 2.2 4.27 0.498 0.491 1.12 2016 [1] ITO/PEDOT:PSS/Sn-HP/ICBA/Bphen/Ag  FA0.55MA0.25Cs0.1PMA0.1SnBr2I PMA mixed 1.93 8.804 0.975 71.12 6.2 2024 [2] FTO/m/c-TiO2/ Sn-HP/spiro-OMeTAD /Au MASnIBr2 Additive SnF2 1.75 13.78 0.45 0.573 3.70 2017 [3] ITO/PEDOT:PSS/Sn-HP/ /PCBM/PEI/Au FASnI2Br Additive SnF2 1.55 19.82 0.60 0.64 7.61 2020 [4] ITO/PEDOT:PSS/Sn-HP/ICBA/BCP/Ag CsSnBr3 Additive SnF2 1.79 13.96 0.37 0.594 3.04 2017 [5] FTO/TiO2/Al2O3/Sn-HP/Carbon CsSnIBr2 Additive HPA 1.63 17.4 0.35 0.55 3.20 2016 [6] FTO/PEDOT:PSS/Sn-HP/ICBA/Bphen/Ag (FA,MA)SnI2Br Interface KSCN 1.63 20.88 0.82 0.64 11.17 2022 [7] ITO/PEDOT:PSS/Sn-HP/ICBA/BCP/Ag EDA(FAMA)SnI2Br Interface 4F-BCl 1.63 13.41 0.94 0.86 11.03 2023 [8] ITO/PEDOT:PSS/Sn-HP/ICBA/BCP/Ag GA0.06(FA0.8Cs0.2)0.94SnI2Br Additive GeI2/EDABr2 1.62 13.74 0.66 0.53 4.86 2022 [9] FTO/PEDOT:PSS/Sn-HP/C60/BCP/Ag GA0.06(FA0.8Cs0.2)0.94SnI2Br Bulk interface  EDA 1.63 15.16 0.64 0.72 7.50 2021 [9] ITO/PEDOT:PSS/Sn-HP/ETL/Ag PEA0.15FA0.75MA0.1SnI2Br Additive PEABr 1.66 16.89 0.67 0.703 7.96 2022 [10] ITO/PEDOT:PSS/2PACz/Sn-HP/C60/BCP/Ag EDA0.01(GA0.06(FA0.8Cs0.2)0.94)0.98SnI2Br HTL interface  1.62 16.22 0.74 0.73 8.66 2022 [11] ITO/PEDOT:PSS/Sn-HP/ICBA/BCP/Ag PEA0.15FA0.75MA0.1SnI2Br Bulk interface F-BHZ  1.68 14.37 1.024 0.757 11.14 2024 This work  S-8            Figure S8. Schematic illustration: a) Energy levels constructed from UPS data (Fig. 3a-d). b) Energy band diagram of WB-Sn-PSC extracted from experimental results.           S-9     Figure S9. (a) J-V results of WB-Sn-PSCs with ICBA and PCBM as ETL. Here, filled/unfilled symbols stand for forward/reverse scan direction. Energy band diagram of WB-Sn-PSC with ETL: PCBM and ICBA.  Table R3. Summary of device parameters of the WB-Sn-PSCs (control and ST) with ICBA and PCBM as ETL. Device structure: ITO/PEDOT:PSS/WB-Sn-HP/ICBA/BCP/Ag ITO/PEDOT: PSS/WB-Sn-HP/PCBM/BCP/Ag Device Scan  direction JSC (mAcm-2) VOC (V) FF PCE (%) JSC (mAcm-2) VOC (V) FF PCE (%) Control F 12.58 0.914 0.692 7.96 10.77 0.851 0.697 6.39 R 12.76 0.928 0.622 7.37 11.16 0.863 0.656 6.32 ST F 14.37 1.024 0.757 11.14 12.95 0.959 0.717 8.90 R 14.46 1.036 0.696 10.43 13.41 0.967 0.706 9.15  S-10              Figure S10. XPS survey and individual spectra of WB-Sn-HP films; (a, b) control and (c, d) FHZ additive. 1st and 2nd spectra represent spectra obtained from the film surface and depth, respectively.     S-11        Figure S11. ToF-SIMS elemental depth profiles of the ITO/Sn-HP films; (a) control and (b) ST. There are selected ionic species; ITO (InO2-), PEDOT:PSS (C8H7SO3–), Sn-HP (Sn+, FA+, MA+, PEA+, F-, Cl-, Br-, I-, and IPL (4F-BHZ).    Figure S12. Fitting of TPC curves (Fig. 4b): a) regime I and b) regime II.   S-12   Figure S13. Admittance analysis of WB-Sn-PSCs; a) Carrier profile extracted from C–V curves. b) C–f spectra under illumination.             Figure S14. (a)Top and (b)side view of the SnI2-terminated surface of the slab model 1. The blue and red colored × in Fig.(a) represent the initial adsorption side of the molecule.      S-13             Figure S15. (a) Top view and (b) side view of the optimized structure of Model2, with the standing molecule on the side on the substrate as the initial position. The adsorption energy is -0.62 eV/system, and the F-Sn bond length is 2.78Å.           Figure S16. (a) Top view and (b) side view of the optimized structure of Model3, with the molecule laying on the back of the substrate as the initial position. The adsorption energy is -1.27 eV/system, and the O-Sn bond length is 2.41Å.    Model 2 : with a molecule laying on the back(a)                                           (b)SnICHNFOModel 4 : with a standing molecule(a)                                           (b)S-14           Figure S17. (a) Top view and (b) side view of the optimized structure of Model4, with the molecule laying on the side on the substrate as the initial position. The adsorption energy is -1.47 eV/system, and the O-Sn bond length is 2.34Å.   Figure S18. Top view of iodine vacancy model (a) and F-BHZ molecules laying on the surface and corresponding side view without (c) and with the molecule (d). The atom-projected density of states without (e) and with the molecule (f) for iodine vacancy defect surface. Where the Fermi energy is set at energy zero (at Fermi energy at CBM).  Model 3 : with a molecule laying on the side(a)                                           (b)S-15  References [1] M. Kaleli, E. Şen, H. E. Lapa, D. A. Aldemir, Physica B Condens Matter 2022, 645, 414293. [2] C.-H. Kuan, Y.-C. Chen, S. Narra, C.-F. Chang, Y.-W. Tsai, J.-M. Lin, G.-R. Chen, E. W.-G. Diau, ACS Energy Lett 2024, 9, 2351. [3] M. Xiao, S. Gu, P. Zhu, M. Tang, W. Zhu, R. Lin, C. Chen, W. Xu, T. Yu, J. Zhu, Adv Opt Mater 2018, 6,1700615. [4] J. Zhang, J. Qin, T. Wu, B. Hu, J Phys Chem Lett 2020, 11, 6996. [5] T. Bin Song, T. Yokoyama, C. C. Stoumpos, J. Logsdon, D. H. Cao, M. R. Wasielewski, S. Aramaki, M. G. Kanatzidis, J Am Chem Soc 2017, 139, 836. 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