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[aenm202202029-sup-0001-suppmat.pdf](https://mdr.nims.go.jp/filesets/aa21d758-1b17-4a4e-9a92-bab37224d68e/download)

## Creator

[Dhruba B. Khadka](https://orcid.org/0000-0001-9134-3890), [Yasuhiro Shirai](https://orcid.org/0000-0003-2164-5468), [Masatoshi Yanagida](https://orcid.org/0000-0002-8065-7875), [Terumasa Tadano](https://orcid.org/0000-0002-8132-2161), [Kenjiro Miyano](https://orcid.org/0000-0002-5869-3087)

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[Creative Commons BY-NC-ND Attribution-NonCommercial-NoDerivs 4.0 International](https://creativecommons.org/licenses/by-nc-nd/4.0/)

## Other metadata

[Interfacial Embedding for High‐Efficiency and Stable Methylammonium‐Free Perovskite Solar Cells with Fluoroarene Hydrazine](https://mdr.nims.go.jp/datasets/8194f5f9-6b54-481e-a881-cc9a98f08056)

## Fulltext

Supporting Informationfor Adv. Energy Mater., DOI: 10.1002/aenm.202202029Interfacial Embedding for High-Efficiency and StableMethylammonium-Free Perovskite Solar Cells withFluoroarene HydrazineDhruba B. Khadka,* Yasuhiro Shirai,* MasatoshiYanagida, Terumasa Tadano, and Kenjiro MiyanoS-1  Supporting Information Interfacial Embedding for High-Efficiency and Stable Methylammonium-Free Perovskite Solar Cells with Fluoroarene Hydrazine Dhruba B. Khadka1*, Yasuhiro Shirai1#, Masatoshi Yanagida1, Terumasa Tadano2, and Kenjiro Miyano1   1 Photovoltaic 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  2 Research Center for Magnetic and Spintronic Materials, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.  Corresponding Author *KHADKA.B.Dhruba@nims.go.jp *SHIRAI.Yasuhiro@nims.go.jp                        S-2  Table and Figures  Figure S1. SEM images of MA-free (FA0.84 Rb0.04Cs0.12PbI3) films with 5F-PHZ treatment; 5F-PHZ solutions in IPA; (a) control, (b) 0.5 mol%, (c) 1 mol%, (d) 2 mol%, (e) 3 mol %, (f) 5 mol%, (g) 10 mol %.    Figure S2. XRD patterns (a) of PbI2 film, control HaP film, perovskite film prepared using 5F-PHZ/perovskite-mixed precursor, and HaP film with 5F-PHZ (dissolved10 mol% in IPA) treatment. (b) absorption spectra respective perovskite films. Here,- PbI2 peak, ∗- 𝛿-perovskite phase, and # -2D phase with 5F-PHZ. The shoulder response marked with # in absorption spectra stem from 2D phase S-3  formed with 5F-PHZ. Note that 5F-PHZ and HaP- mixed precursor was prepared by mixing 0.5M-5F-PHZ + 0.5 M PbI2 and 1M of control precursor (FA0.84 Rb0.04Cs0.12PbI3).       Figure S3. J-V characteristics of PSCs with 3D-perovskite film; FA0.84 Rb0.04Cs0.12PbI3, treated with 5F-PHZ-IPA solution with varying concentrations. (0-10 mol%). The double line of J-V curves for each case represents forward and reverse scan directions.   Figure S4. Photographs of a set of complete HaP devices prepared on ITO substrate (4.5 cm ×3.5 cm) and scale of each device size (1cm×1cm) used for measurement mask. S-4    Figure S5. Statistics of photovoltaic parameters of control and with 5F-PHZ treatment PSCs, including VOC, JSC, FF, and PCE. These data consist of 30 devices from 5 batches for each 5F-PHZ concentration.    Figure S6. Certified results from an accredited photovoltaic certification laboratory (AIST, Japan). The certified J-V curves (RB-HaP film: Rb0.4Cs0.12FA0.84PbI3 with 5F-PHZ surface treatments) with S-5  double scanning give PCE forward: 20.77% and PCE reverse: 21.01% with large device area of 1.026 cm2.   Table S1. Summary of certified/record device large area (1 cm2) reports (Pb-perovskite using multiple cations, anions, functional additives, and interfacial layer).  Device Type Device Structure Perovskite Additive Area (cm2) PCE (%) Reported Efficiency date Ref. Regular (n-i-p) Glass/ITO/c-TiO2/TiO2 nanorods/PMMA:PCBM/ Perovskite/PMMA/Spiro-OMeTAD)/MoOx/IZO/Au (Cs,FA,MA)Pb(I,Br)3 ----- 1.0 21.6 Certified 2021 [1] Regular (n-i-p) Glass/FTO/TiOxNy/meso-TiO2/PMMA: PCBM/ perovskite/PMMA/P3HT: CuPc/Au (Cs,FA,MA)Pb(I,Br)3 0.01 M-PbCl2, 0.01 M-MACl 1.0 22.6 Certified 2022  [2] Regular (n-i-p) Glass/FTO/SnO2/ perovskite/spiro-OMeTAD/EVA/Cu-Ni-Graphene FAMAPb(I,Br)3 ----- 0.09 24.37  Certified 2022  [3] 1.02 20.76  Inverted (p-i-n) Glass/ITO/NiOx-nanoparticles/ (IL)EMDP/ Perovskite/PCBM/BCP/Au (Cs,FA,MA)Pb(I,Br)3 ----- 1.01 20.91 Not certified 2021  [4] Regular (n-i-p) Glass/FTO/SnO2(ALD)/PCBM/PMMA/Perovskite/PMMA/Spiro/Au  (Rb,Cs,FA)PbI3 ----- 0.1024 20.35 Not certified 2018  [5] Inverted (p-i-n) Glass/ITO/2PACz/Perovskite/PEACl/C60/BCP/Au (Cs,FA)PbI3  phenethylammonium chloride 0.123 22.3 Not certified 2021 [6] Inverted (p-i-n) Glass/ITO/NiOx-sputtered/MeO/Perovskite/5F-PHZ/C60/BCP/Ag (Rb,Cs,FA)PbI3 5F-PHZ 1.026 21.01 (22.29) Certified  *This work (Record certify PCE for inverted device structure)          S-6         Figure S7. Estimation of bandgap energy (Eg) of HaP layer in control and 5F-PHZ PSCs. (a) Eg estimated from EQE analysis and (b) Eg calculated from absorption spectra of respective films.                  S-7        Figure S8. XPS-spectra for the control and 5F-PHZ treated films; I-3d core (a), Cs-3d core (b), and Rb-3d core (c). Arrow head indicates shifting direction of XPS characteristic peak.      Figure S9. XPS-spectra for the control and 5F-PHZ treated films. F-1s core with Depth profile of 5F-PHZ treatment (a). A comparison of XPS spectra control, 5F-PHZ (optimal, 3 mol%) and 5F-PHZ (5 mol%); F-1s core (b), C-1s core (c), Cs-3d (d), Pb-4f core (e), and I-3d core (f). Arrowhead indicates shifting direction of XPS characteristic peak.     S-8   Figure S10. Cross-sectional HR-TEM image of RB-PSCs; control (a1) and 5F-PHZ treatment (b1). Interface of C60/HaP (a2, b2) and the interface of C60/HaP top surface (a3, b3). Note that 2D-phase formed with 5F-PHZ distributes unevenly on the surface of 3D-HaP or at grain boundaries.    Figure S11. STEM-EDX mapping of the control (a) and 5F-PHZ treated device for RB-PSCs (b). The EDX mapping of respective layer is displayed in respective row. ITO- In (a2, b2), NiOx-Ni (a3, b3), HaP; -I (a4, b4), Pb (a5, b5), Cs (a6, b6), Rb (a7, b7), PCBM- C (a8, b8), Ag-electrode-Ag (a9, b9).   S-9    Figure S12. Differentiation of C-f spectra for determination of inflection frequencies; control device (a) and 5F-PHZ treated device (b).   Figure S13. Atomic structures and associated density of states (DOS) of 5F-PHZ passivated surfaces obtained from DFT calculations. (a) Side views of the (meta-)stable structures of a 5F-PHZ molecule on PbI2-terminated surface with an IPb antisite defect. The struct. 1 is the most stable structure we obtained, and other three structures are less stable by the energy values shown in the parentheses. (b) Calculated DOS of the four structures shown in (a). For the pristine and the 5F-PHZ passivated surfaces, the energy (x-axis) is measured relative to their valence band maximum. For the IPb defected surface, the x-axis value is slightly adjusted in such a way that the position of the conduction band minimum, which is calculated after neglecting the in-gap state, matches with that of the pristine surface. In the main text, we show the results for the most stable structure (struct. 1).  S-10     Figure S14. J-V curves (device parameters Table S2) (▼forward /s reverse scan direction) of control, PHA, and 5F-PHZ treated devices measured under AM 1.5G illumination for RB-HaP; Rb0.04Cs0.12FA0.84PbI3.  Table S2. Photovoltaic parameters of the best performing RB-PSCs (control, PHA, and 5F-PHZ treatment). F and R- scan stand for forward and reverse scan directions. The statistical data (control, PHA, and 5F-PHZ treatment) are taken from 16 devices (average (avg) and standard deviation (sd)) from 4 batches. Device parameters RB-HaP: Rb0.04Cs0.12FA0.84PbI3 - RB-PSCs Control PHA 5F-PHZ Best result Statistics (avg ±sd) Best result Statistics (avg ±sd)  Statistics (avg ±sd) F-scan R-scan   F-scan R-scan  F-scan R-scan  JSC (mA/cm2) 22.874 22.88 22.67 ±0.34 23.28 23.24 23.03 ±0.34 24.55 24.51 24.05  ±0.37 VOC (V) 1.098 1.096 1.09 ±0.015 1.101 1.105 1.10 ±0.035 1.1765 1.178 1.163 ±0.011 FF 0.6952 0.722 0.692 ±0.0185 0.734 0.752 0.731 ±0.0286 0.761 0.772 0.752 ±0.0164 Rs (𝛺cm-2) 5.41 5.23   5.7 5.52   4.96 4.90   Rsh (k𝛺cm-2) 2.55 5.37   3.21 8.51   3.51 7.88   PCE (%) 17.45 18.10 17.26 ±0.64 18.81 19.31 19.12 ±0.62 21.98 22.29 21.03 ±0.65  S-11   Figure S15. Schematic of device architecture (ITO/PEDOT:PSS/NB-HaP/C60/BCP/Ag) (a). J-V curves (device parameters Table S3) (b) (▼forward /s reverse scan direction). EQE spectra (c) of control and 5F-PHZ treated devices measured under AM 1.5G illumination for NB-HaP; Sn-Pb-HaP; FA0.85MA0.1Cs0.05(Pb0.5Sn0.5)I3. The values of integrated JSC extracted from EQE spectra; 29.80 and 30.64 mAcm-2. Diode ideality factor extracted from intensity dependent-VOC (d). Estimation of bandgap energy (Eg) of NB-HaP layer in control and 5F-PHZ PSCs from the absorption spectra (e) and EQE analysis (f).  Table S3. Photovoltaic parameters of the best performing NB-PSCs (control and 5F-PHZ treatment). F and R- scan stand for forward and reverse scan directions. The statistical data (control or 5F-PHZ treatment) are taken from 16 devices (average (avg) and standard deviation (sd)) from 4 batches. Device parameters NB-HaP: FA0.85MA0.1Cs0.05(Pb0.5Sn0.5)I3- NB-PSCs Control 5F-PHZ best result statistics (avg±sd) best result Statistics (avg±sd) F-scan R-scan  F-scan R-scan  JSC (mA/cm2) 30.68 30.72 30.36 ±0.52 31.08 31.16 30.86 ±0.36 VOC (V) 0.743 0.758 0.741 ±0.013 0.821 0.831 0.813 ±0.011 FF 0.631 0.722 0.663 ±0.038 0.711 0.747 0.72 ±0.021 Rs (𝛺cm-2) 3.33 2.98  2.94 2.92  Rsh(k𝛺cm-2) 5.93 15.14  24.77 38.42  PCE (%) 14.38 16.81 15.23 ±0.98 18.14 19.34 18.74 ±0.57 S-12     Figure S16. Schematic of device architecture (WB-PSCs) (ITO/NiOx/MeO-2PACz/WB-HaP/C60MC12/BCP/Ag) (a). J-V curves (device parameters Table S4) (b) (▼forward /s reverse scan direction). EQE spectra (c) of control and 5F-PHZ treated devices measured under AM 1.5G illumination for MA-free wide-bandgap halide perovskite (WB-HaP); FA0.84Cs0.12Rb0.04Pb(I0.63Br0.37)3 system. The values of integrated JSC extracted from EQE spectra; 17.72 and 18.39 mAcm-2. Estimation of bandgap energy (Eg) of WB-HaP layer in control and 5F-PHZ PSCs from the EQE analysis (d). For WB-PSCs, we adopted the halide composition as reported by Snaith and co-workers[7] and our previous report.[8] Similarly, the ETL layer; C60-fused N-methylpyrrolidine-meta-dodecyl phenyl (C60MC12) was used as reported in our earlier report for WB-PSC.[8]  Table S4. Photovoltaic parameters of the best performing WB-PSCs (control and 5F-PHZ treatment). F and R- scan stand for forward and reverse scan directions. The statistical data (control or 5F-PHZ treatment) are taken from 16 devices (average (avg) and standard deviation (sd)) from 4 batches. S-13      Figure S17. Operational stability of the control and 5F-PHZ treated devices (RB-HaP; Eg~1.52 eV). The devices were kept under 1-Sun intensity under MPPT conditions (35–40% RH, 27–32 °C~RT (a, c) and elevated temperature ~65 °C (b, d)) during device stability monitoring.    Device parameters WB-HaP: FA0.84Cs0.12Rb0.04Pb(I0.63Br0.37)3- WB-PSCs Control 5F-PHZ best result statistics (avg±sd) best result Statistics (avg±sd) F-scan R-scan  F-scan R-scan  JSC (mA/cm2) 18.75 18.24 17.82±0.56 19.32 19.28 19.18 ±0.114 VOC (V) 1.234 1.241 1.240 ±0.0041 1.282 1.283 1.279 ±0.0034 FF 0.649 0.739 0.707 ±0.033 0.737 0.765 0.74 ±0.016 Rs (𝛺cm-2) 5.92 5.53  4.69 4.81  Rsh (k𝛺cm-2) 2.48 3.62  5.74 11.18  PCE (%) 15.01 16.73 15.62 ±0.71 18.27 18.92 18.32 ±0.42 S-14   Figure S18. Operational stability of the control and 5F-PHZ treated devices (RB-HaP; Eg~1.52 eV). The devices were kept under 1-Sun intensity under MPPT conditions (60–65% RH, 27–32 °C~RT) (a). Images of the water contact angle on the surface of (b) control and (c) 5F-PHZ treated perovskite films at different water loading times (initial (0 min) and after 1 min).   References [1] J. Peng, D. Walter, Y. Ren, M. Tebyetekerwa, Y. Wu, T. Duong, Q. Lin, J. Li, T. Lu, M. A. Mahmud, O. L. C. Lem, S. Zhao, W. Liu, Y. Liu, H. Shen, L. Li, F. Kremer, H. T. Nguyen, D.-Y. Choi, K. J. Weber, K. R. Catchpole, T. P. White, Science 2021, 371, 390. [2] J. Peng, F. Kremer, D. Walter, Y. Wu, Y. Ji, J. Xiang, W. Liu, T. Duong, H. Shen, T. Lu, F. Brink, D. Zhong, L. Li, O. Lee Cheong Lem, Y. Liu, K. J. Weber, T. P. White, K. R. Catchpole, Nature 2022, 601, 573. [3] X. Lin, H. Su, S. He, Y. Song, Y. Wang, Z. Qin, Y. Wu, X. Yang, Q. Han, J. Fang, Y. Zhang, H. Segawa, M. Grätzel, L. Han, Nat. Energy 2022, DOI 10.1038/s41560-022-01038-1. [4] S. Zhang, H. Wang, X. Duan, L. Rao, C. Gong, B. Fan, Z. Xing, X. Meng, B. Xie, X. Hu, Adv. Funct. Mater. 2021, 31, 2106495. [5] S.-H. Turren-Cruz, A. Hagfeldt, M. Saliba, Science 2018, 362, 449. [6] S. Gharibzadeh, P. Fassl, I. M. Hossain, P. Rohrbeck, M. Frericks, M. Schmidt, T. Duong, M. R. Khan, T. Abzieher, B. A. Nejand, F. Schackmar, O. Almora, T. Feeney, R. Singh, D. Fuchs, U. Lemmer, J. P. Hofmann, S. A. L. Weber, U. W. Paetzold, Energy Environ. 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