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## 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), [Hitoshi Ota](https://orcid.org/0000-0002-8339-9592), [Andrey Lyalin](https://orcid.org/0000-0001-6589-0006), Tetsuya Taketsugu, [Kenjiro Miyano](https://orcid.org/0000-0002-5869-3087)

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[Creative Commons BY Attribution 4.0 International](https://creativecommons.org/licenses/by/4.0/)

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[Defect passivation in methylammonium/bromine free inverted perovskite solar cells using charge-modulated molecular bonding](https://mdr.nims.go.jp/datasets/4051e175-caf9-4d80-9db7-99ccdab82c9d)

## Fulltext

S-1  Supplementary Information  Defect Passivation in Methylammonium/Bromine Free Inverted Perovskite Solar Cells Using Charge-Modulated Molecular Bonding  Dhruba B. Khadka1*, Yasuhiro Shirai1*, Masatoshi Yanagida1, Hitoshi Ota2, Andrey Lyalin3,4*, Tetsuya Taketsugu4,5, 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  2Battery Research Platform, Research Center for Energy and Environmental Materials (GREEN), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba 305-0044, Japan 3Research Center for Energy and Environmental Materials (GREEN), National Institute for Materials Science, Namiki 1-1, Tsukuba 305-0044, Japan 4Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan 5Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan  Corresponding Author *KHADKA.B.Dhruba@nims.go.jp *SHIRAI.Yasuhiro@nims.go.jp *lyalin@icredd.hokudai.ac.jp                 mailto:KHADKA.B.Dhruba@nims.go.jpS-2  Supplemenatry Tables and Supplementary Figures     Fig. S1. XRD patterns of MA-free (FA0.84 Rb0.04Cs0.12PbI3) films without and with DIM treatments: a) PEDAI or b) PZDI solutions in IPA; 0 (control), 0.5, 1, and 2 mg/ml. c, d) Absorption spectra of respective films.                S-3       Fig. S2. PL spectra of HP films without and with DIM treatments: a) PEDAI or c) PZDI solutions in IPA; 0 (control), 0.5, 1, and 2 mg/ml. b, d) represent normalized PL spectra of respective films.         S-4   Fig. S3. Photo of mixed HP precursor [ a1) PEDAI or b1) PZDI and HP/mixed precursor]. a2, b2) XRD patterns of PbI2 film, HP film surface treated with PEDAI or PZDI (dissolved 2 mg/ml in IPA), HP film with mixed PEDAI or PZDI, and powder crystal prepared by mixing PbI2 and PEDAI or PZDI in 1:2 ratio. Here, # -2D phase with PEDAI or PZDI, - PbI2 peak, 𝛿- non-photoactive perovskite phase, α- photoactive perovskite phase. a3, b3) SEM images of HP film (mixed precursor: PEDAI or PZDI/perovskite-mixed precursor. c) PL spectra of the HP film prepared using mixed precursor. The shoulder response marked with # in PL spectra stems from the 2D phase formed with PEDAI or PZDI. Note that mixed precursor was prepared by mixing 0.5 M-PEDAI or PZDI + 0.5 M PbI2 and 1M of control precursor (FA0.84 Rb0.04Cs0.12PbI3).   Fig. S4. a) Schematic of synthesis of single crystal by antisolvent vapor-assisted crystallization method. of single crystal sample. b) the vial containing precursor solution was sealed in a bottle and crystal growth (displayed in the rectangle) and crystal separated from the vial.  S-5   Fig. S5. Analysis of a single crystal obtained by adopting the method as depicted in Fig. S4. a1) simulated PXRD result of crystal (insets are optical image, dimension, and composition: (Single-crystal structure of PZDI)2(PbI4)2. 6DMSO (CCDC 2311444)) grown in precursor solution (mixing PZDI and PbI2 in 2:1 molar ratio), a2) simulated crystal unit, a3) Packing diagram. b1-b3) corresponding results and properties of the single-crystal structure of PZDI)3Pb2I7. 6DMSO (CCDC 2311446) as grown in precursor solution (mixing PZDI and PbI2 in 1:1 molar ratio).                  S-6  Table S1. Crystal data and refinement of a corresponding single crystal ((PZDI)2(PbI4)2. 6DMSO: CCDC 2311444 and (PZDI)3Pb2I7. 6DMSO: CCDC 2311446). Crystal data XRD- patterns- Fig. S5a1 XRD- patterns- Fig. S5b1 CIF file CCDC 2311444 CCDC 2311446 Chemical Formula (PZDI)2(PbI4)2. 6 DMSO (PZDI)3Pb2I7. 6 DMSO Formula weigh 1037.33 1903.68 Crystal size (mm) 0.354 × 0.192 × 0.089 0.45 × 0.22 × 0.14 𝝁 (mm-1) 11.055 10.968 Radiation type Mo Kα Mo Kα Wavelength (Å) 0.71073 0.71073 Temperature 293(2) 293.00(10) Crystal system Orthorhombic Monoclinic Space group Pna21 P 21 /n a, b, c (Å) 20.3941 (3), 13.7425 (2), 19.2851 (3) 19.4940(3), 14.11900(10), 20.1039(2) a, b, g (°) 90, 90,90 90, 111.049(2), 90 V (Å3 ) 5404.96 (14) 5164.09(12) Z 8 4 Data collection No. of measured 134993 170497 No. of independent 14685 14425 Completeness 1 0.876 Rint 0.0498 0.0613 2θmax (°) 61.818 61.998 Refinement R1 [F2 > 2s (F2 )] 0.0439 0.0395 wR(F2 ) 0.0978 0.0836 S 1.149 1.167 No. of reflections 14685 14425 No. of parameters 475 435      S-7   Fig. S6. Photographs of a set of HHPSC devices prepared on ITO substrate (4.5 cm ×3.5 cm) and scale of each device size (1cm×1cm) used for measurement mask.  Fig. S7. J-V curves of the control and DIM; a) PEDAI or b) PZDI treated HPSCs. ▼/ forward /reverse scan direction.    S-8   Fig. S8. Statistics of PV characteristic parameters of control and PEDAI or PZDI-treated HPSCs, including; a) VOC, b) JSC, c) FF, and d) PCE. The data shown above the box distribution corresponds average and standard deviation for corresponding device parameters. These data consist of 50 devices from 6 batches.       S-9   Fig. S9. Statistics of PV characteristic parameters of control and PEDAI-treated HPSCs, including; a) VOC, b) JSC, c) FF, and d) PCE. These data consist of 30 devices from 4 batches.  Table S2. Photovoltaic parameters of the best-performing HPSCs with MA-free HP (without and with PEDAI surface treatment). The parameters given inside the parentheses represent the average values and standard deviation.           Device/parameters Control 0.5 mg/ml 1 mg/ml 2 mg/ml JSC (mAcm-2) 23.56 (23.41 ±0.21) 22.75 (22.91±0.26) 22.73 (22.66±0.31) 22.67 (23.51±0.27) VOC (V) 1.112 (1.089 ±0.016) 1.132 (1.118 ±0.014) 1.145 (1.131 ±0.013) 1.142 (1.114 ±0.022) FF 0.750 (0.725 ±0.014) 0.745 (0.726 ±0.016) 0.738 (0.725 ±0.016) 0.702 (0.701 ±0.013) PCE (%) 19.64 (18.51 ±0.48) 19.18 (18.61 ±0.394) 19.22 (18.89 ±0.48) 18.17 (17.49 ±0.46) S-10    Fig. S10. Statistics of PV characteristic parameters of control and PZDI treated HPSCs, including; a) VOC, b) JSC, c) FF, and d) PCE. These data consist of 30 devices from 4 batches.   Table S3. Photovoltaic parameters of the best-performing HPSCs with MA-free HP (without and with PZDI surface treatment). The parameters given inside the parentheses represent the average values and standard deviation.        Device/parameters Control 0.5 mg/ml 1 mg/ml 2 mg/ml JSC (mAcm-2) 23.56 (23.41 ±0.21) 24.63 (23.97 ±0.42) 24.79 (24.15 ±0.51) 24.54 (23.71 ±0.43) VOC (V) 1.112 (1.089 ±0.016) 1.181 (1.663 ±0.009) 1.186 (1.176 ±0.008) 1.174 (1.168 ±0.011) FF 0.750 (0.725 ±0.014) 0.765 (0.762 ±0.006) 0.784 (0.775 ±0.012) 0.756 (0.752 ±0.013) PCE (%) 19.64 (18.51 ±0.48) 22.25 (21.27 ±0.39) 23.05 (22.35 ±0.54) 21.78 (20.95 ±0.49) S-11     Fig. S11. Certified results from an accredited photovoltaic certification laboratory (AIST, Japan). The certified PCE is 21.36% - certified aperture with an area of ~1.024 cm2. The certified J-V curves with double scanning give PCE forward: 21.20% and PCE reverse: 21.47%. (HP film: Rb0.4Cs0.12FA0.84PbI3 with PZDI surface treatment).       S-12  Table S4. Summary of certified/record device large area (1 cm2) reports (Pb-HP 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) 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) FTO/TiOxNy/meso-TiO2/PMMA: PCBM/ perovskite/PMMA/P3HT: CuPc/Au (Cs,FA,MA)Pb(I,Br)3 0.01 M-PbCl2/MACl 1.0 22.6 Certified 2022  2 Regular (n-i-p) 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) ITO/NiOx-nanoparticles/ (IL)EMDP/ Perovskite/PCBM/BCP/Au (Cs,FA,MA)Pb(I,Br)3 ----- 1.01 20.91 Not certified 2021  4 Inverted (p-i-n) ITO/PTAA/PIC-Al2O3/ Perovskite/C60/BCP/Ag (FA,MA)CsPb(I,Br)3 MACl 0.06 24.9 certified 2023 5 1.06 23.30  Regular (n-i-p) ITO/SnO2/perovskite/Spiro-OMeTAD/Au (Cs,FA)PbI3  4-MeO-PEAI 1.00  23.7 certified 2022 6 Regular (n-i-p) FTO/SnO2/perovskite/ Spiro-OMeTAD/ Au (Cs,FA,MA)Pb(I,Br,Cl)3 2-Cl-PEAI 0.1 23.9 certified 2023 7 1.00 23.7 Regular (n-i-p) FTO/SnO2(ALD)/PCBM/PMMA/Perovskite/PMMA/Spiro/Au  (Rb,Cs,FA)PbI3 ----- 0.1024 20.35 Not certified 2018 8 Regular (n-i-p) FTO/TiO2/perovskite/ Spiro-OMeTAD/ Au (Cs,FA)PbI3 CoFAc 0.09 24.64 Not certified 2023 9 Inverted (p-i-n) ITO/2PACz/Perovskite/PEACl/C60/BCP/Au (Cs,FA)PbI3  PEACl 0.123 22.3 Not Certified 2021 10 Inverted (p-i-n) ITO/NiOx-iink/Perovskite/C60/BCP/Cu (Cs,FA,)Pb(I,SCN)3 TCMAI-doping 0.04 23.2 Certified 2023 11 Inverted (p-i-n) ITO/NiOx-sputtered/MeO/Perovskite/PZDI/C60/BCP/Ag (Rb,Cs,FA)PbI3 PZDI 1.024 21.47 (23.17) Certified  *This work (Record certify PCE for inverted device structure)    S-13     Fig. S12. Estimation of bandgap energy (Eg) of HP layers (control and with surface treatment (PEDAI or PZDI)). a-c) Eg estimated from EQE analysis. d-f) Eg calculated from absorption spectra of respective films.          S-14    Fig. S13. Energy band schematics of control and PEDAI or PZDI treated film extracted from UPS spectra. Note that Eg for this schematic is calculated from absorption spectra (ｓFig. S12d-f).     Fig. S14. XPS-spectra for the control and PEDAI or PZDI treated films; a) I-3d core, b) Pb-4f, c) Cs-3d core, and d) Rb-3d core. The arrowhead indicates the shifting direction of the XPS Characteristic peak.    S-15   Fig. S15. Cross-sectional HR-TEM image of HPSCs for interface analysis; control (a1-a4), PEDAI-treated (b1-b4), and PZDI-treated (c1-c4). HP/NiOx interface (a1,b1,c1)), over all cross-section (a2,b2,c2), C60/HP interface ((a3,b3,c3), and interface of C60/HP top surface (a4,b4,c4). Note that the surface passivation with PEDAI forms a rich 2D phase at the interface and grain boundaries. On the other hand, PZDI surface treatment grows with an evenly distributed 2D phase interface on the surface of 3D-HP with diffusion through grain boundaries to some extent.  S-16   Fig. S16. ToF-SIMS depth profiles of control and surface-treated HP film. a) PEDA2+ distribution and b) PZD2+ distribution in control and DIM-treated HP films. Reconstructed 3D maps; Distributions of passivated molecules in HP film c) control, d) PEDAI-treated, and e) PZDI-treated.      Fig. S17. XRD spectrum at different tilt angles for a) control, b) PEDAI, and c) PZDI devices, respectively. d) Residual strain extracted from the corresponding HPSC device’ diffraction strain data as a function of sin2ψ.     S-17       Fig. S18. GIXRD spectra: a, d) control, b, e) PEDAI, and c, f) PZDI.  g) plot of penetration depth corresponds to the grazing incident angle. X-ray attenuation length (penetration depth) into the perovskite film (estimated density ~3.86 gcm-3) was calculated using a report by Davis and co-workers ( Atomic Data and Nuclear Data Tables, 1993, 54, 181-342) and Rigaku-manual.          S-18      Fig. S19. Thermal admittance spectra (TAS). a1-c1) C-f-T spectra of control and PEDAI or PZDI treated devices. a2-c2) differentiation of respective C-f-T spectra for determination of inflection frequencies.             S-19    Fig. S20. The optimized pseudo-cubic structure of the bulk FAPbI3. Pb atoms are colored grey, I atoms are purple, C atoms are brown, N atoms are light grey, and H atoms are light pink. The orientation of the lattice axes (a/b/c and arrows) is shown in the insert. Figure was created using VESTA software.12    Fig. S21. a) The optimized structure of the 2x2 unit cell of PbI2-terminated surface (001) of the pseudo-cubic FAPbI3. b) Total density of states calculated for the defect-free PbI2-terminated surface of FAPbI3. The orientation of the lattice axes (a/b/c and arrows) is shown in the insert.  Figure in (a) was created using VESTA software.12  S-20   Fig. S22. The optimized structures of a free 1,4-phenylenediamine dihydriodide (PEDAI), C6H8N2*2HI, molecule. (a) The most stable trans-isomer structure, and (b) the low-energy cis-isomer form. Mulliken charges or Mulliken charges with summed H (iodine and nitrogen atoms) were calculated at the B3LYP/def2TZVP level of theory with the use of Gaussian 09.17  Free 1,4-phenylenediamine dihydriodide (PEDAI), C6H8N2*2HI, molecules possess several isomeric forms depending on the position of the HI compounds. The most stable trans-isomer is shown in Figure S18a, while its cis form (Fig. S22b) is only 0.086 eV less stable. When PEDAI adsorbs on the PbI2-terminated surface of FAPbI3 adsorption of the cis-form became energetically favorable, as it maximizes interaction of I atoms of PEDAI with the surface Pb atoms.  Fig. S23. The optimized structure of a free piperazine dihydriodide (PZDI), C4H10N2*2HI, molecule. Mulliken charges were calculated at the B3LYP/def2TZVP level of theory with the use of Gaussian 09.18    S-21          Fig. S24. Optimized structures of a) PEDAI and b) PZDI adsorbed on the defect-free PbI2-terminated surface of FAPbI3. The spin-polarized total DOS calculated for the PbI2-terminated surface of FAPbI3 covered by c) PEDAI and d) PZDI. The orientation of the lattice axes (a/b/c and arrows) is shown in the insert. Figures in a) and b) were created using VESTA software.12      S-22     Fig. S25. Device characteristics for wide bandgap-HP (Pb-HP; FA0.84Cs0.12Rb0.04Pb(I0.63Br0.37)3) (WB-HP). a) J-V curves (device parameters, Table S5) (filled/open symbol- forward /reverse scan direction) of control and PZDI-treated HPSCs. b) PCE statistics of devices. c) EQE spectra of respective devices. The values of integrated JSC extracted from EQE spectra; 18.22 and 18.78 mAcm-2. (d) Estimation of bandgap energy (Eg) from EQE analysis.   Table S5. Photovoltaic parameters of the best-performing WB-HPSCs corresponding to J-V curves (Fig. S25). F and R- scan stand for forward and reverse scan directions. The statistical data (control or PZDI treatment) are taken from 30 devices (average (avg) and standard deviation (sd)) from 5 batches.    Device parameters WB-HPSCs Control PZDI  statistics (avg±sd)  Statistics (avg±sd) F-scan R-scan  F-scan R-scan  JSC (mA/cm2) 18.86 18.80 18.68 ±0.62 19.43 19.32 19.08 ±0.114 VOC (V) 1.262 1.274 1.26 ±0.003 1.316 1.321 1.312 ±0.002 FF 0.695 0.732 0.709 ±0.004 0.724 0.761 0.724 ±0.017 PCE (%) 16.54 17.53 16.76 ±0.69 18.51 19.42 18.46 ±0.42 S-23     Fig. S26. Device characteristics for narrow bandgap-HP (Sn-Pb-HP; FA0.85MA0.1Cs0.05(Pb0.5Sn0.5)I3) (NB-HP). a) J-V curves (device parameters, Table S6) (filled/open symbol- forward /reverse scan direction) of control and PZDI-treated HPSCs. b) PCE statistics of devices. c) EQE spectra of respective devices. The values of integrated JSC extracted from EQE spectra; 30.19 and 30.86 mAcm-2. d) Estimation of bandgap energy (Eg) from EQE analysis.  Table S6. Photovoltaic parameters of the best-performing NB-HPSCs corresponding to J-V curves (Fig. S26). F and R- scan stand for forward and reverse scan directions. The statistical data (control or PZDI treatment) are taken from 30 devices (average (avg) and standard deviation (sd)) from 5 batches.      Device parameters NB-HPSCs Control PZDI  statistics (avg±sd)  Statistics (avg±sd) F-scan R-scan  F-scan R-scan  JSC (mA/cm2) 31.87 31.15 29.78 ±1.05 31.99 31.46 31.74 ±0.64 VOC (V) 0.784 0.785 0.80 ±0.033 0.858 0.860 0.840 ±0.008 FF 0.669 0.730 0.707 ±0.028 0.697 0.751    0.720 ±0.023 PCE (%) 16.74 17.85 16.96 ±0.77 19.14 20.32 19.17 ±0.56 S-24        Fig. S27. Stability of the control, PEDAI, and PZDI passivated HPSCs. Non-normalized stability data operational tracking under MPPT conditions: T=60 ±5 °C;  RH~ 30–35% (ISOS-L-2) (corresponding to Fig. 6a)   Table S7. Photovoltaic parameters of corresponding aged devices.  Parameters/ Time (h) control device PEDAI treated PZDI treated JSC (mAcm-2) VOC (V) FF PCE JSC (mAcm-2) VOC (V) FF PCE JSC (mAcm-2) VOC (V) FF PCE (%) 0 23.36 1.113 0.751 19.53 22.94 1.142 0.731 19.15 24.54 1.188 0.784 22.86 100 23.56 1.113 0.750 19.67 22.75 1.143 0.716 18.62 24.3 1.188 0.777 22.43 500 20.73 1.113 0.690 15.92 21.9 1.142 0.69 17.26 23.27 1.191 0.767 21.26 1000 15.36 1.114 0.660 11.29 18.55 1.145 0.67 14.23 22.66 1.194 0.756 20.45            S-25            Fig. S28. Stability of the control, PEDAI, and PZDI passivated HPSCs. Non-normalized stability data operational tracking under MPPT conditions: T=35 ±5 °C; RH~ 60–65% (ISOS-L-3) (corresponding to Fig. 6b).   Table S8. Photovoltaic parameters of corresponding aged devices.  Parameters/ Time (h) Control device PEDAI treated PZDI treated JSC (mAcm-2) VOC (V) FF PCE JSC (mAcm-2) VOC (V) FF PCE JSC (mAcm-2) VOC (V) FF PCE (%) 0 23.62 1.104 0.717 19.52 22.98 1.146 0.724 19.07 24.5 1.188 0.788 22.94 100 19.16 1.03 0.52 10.23 21.28 1.145 0.712 17.35 23.74 1.188 0.775 21.86 200 16.16 1.016 0.45 7.38 19.94 1.143 0.69 15.73 23.35 1.189 0.772 21.43 500     17.76 1.144 0.68 13.82 21.81 1.191 0.766 19.90        S-26   References 1. Peng, J. et al. Nanoscale localized contacts for high fill factors in polymer-passivated perovskite solar cells. Science 371, 390–395 (2021). 2. Peng, J. et al. Centimetre-scale perovskite solar cells with fill factors of more than 86 per cent. Nature 601, 573–578 (2022). 3. Lin, X. et al. In situ growth of graphene on both sides of a Cu–Ni alloy electrode for perovskite solar cells with improved stability. Nat Energy 7, 520–527 (2022). 4. Zhang, S. et al. 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