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15 protocols using formamidinium iodide

1

Perovskite Film Preparation and Aging

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The 0.5 M perovskite solution was prepared by dissolving the powders methylammonium bromide (CH3NH3Br; Dyesol), formamidinium iodide (CH(NH2)2I; Sigma Aldrich), lead(II) iodide (PbI2; Sigma Aldrich) and lead bromide (PbBr2; Alfa Aesar) in a mixed solvent of N,N-dimethylformamide (DMF; Sigma Aldrich) and dimethylsulfoxide (DMSO; Sigma Aldrich) at a volume ratio of 4:1. The spray deposition was conducted inside a custom-made chamber in a normal atmosphere. Nitrogen with a pressure of 2 bar was applied as a carrier gas, and the substrate was placed on a heating stage with a temperature of 100 °C. To obtain the defined dimensions, focused ion beam (FIB; Zeiss NVision 40) milling was carried out on the spray-cast perovskite film at a high milling current of 1.6 nA and high acceleration voltage of 30 kV (Ga+ ion source). Afterwards, the samples were stored at ambient conditions for around 30 days without special encapsulations to allow for moisture induced aging.
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2

Perovskite Solar Cell Fabrication

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The following materials were used: formamidinium
iodide (Sigma, >99%), PbI2 (Sigma, 99%), phenylethylammonium
iodide (Greatcell Solar Materials), anhydrous dimethylformamide (99.8%,
Acros), dimethylsulfoxide (99.7%, Acros), acetone (99.6%, Acros),
chlorobenzene (99.8%, Acros), isopropanol (99.5%, Acros), and d5-FAI (Cortecnet, 85% CD deuterated, 90% ND2 deuterated). d4-FAI and d3-PEAI were prepared by dissolving in heavy
water (1:40 mol/mol ratio), followed by evaporation. This yielded
∼50 and ∼70% deuterium on the FAI and PEAI, respectively.
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3

Synthesis of Perovskite Solar Cell Precursors

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Zinc acetate dehydrate (99.999%), aluminum nitrate nonahydrate (99.99%), methanol (anhydrous, 99.8%), potassium hydroxide (KOH, ≥85%), formamidinium iodide (FAI, anhydrous, ≥99%), methylammonium iodide (MAI, anhydrous, ≥99%), lead iodide (PbI2, 99.999%), lead iodide (PbBr2, 99.999%), dimethyl sulfoxide (DMSO, anhydrous, 99.9%), and N,N-dimethylformamide (DMF, anhydrous, 99.8%) were purchased from Sigma-Aldrich.
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4

Perovskite Solar Cell Fabrication

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Lead (II) iodide (PbI2, 99.99%) was purchased from TCI America, while N,N dimethylformamide (DMF), dimethylsulfoxide (DMSO), anhydrous ethanol, toluene, chlorobenzene, methylammonium bromide (MABr), lead (II) bromide (PbBr2), caesium iodide (CsI), methylammonium iodide (MAI, 99.9%), and formamidinium iodide (FAI, > 98%), tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tris-(bis(trifluoromethyl sulfonyl)imide) (FK209). were purchased from Sigma-Aldrich. The 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD) was obtained from Lumtec. Finally, fluorine-doped tin oxide (FTO) coated glass substrates (dimensions: 25 mm × 25 mm × 2.2 mm; sheet resistance: 7–8 Ω sq−1), were purchased from Zhuai Kaivo, China. All chemicals were used as received.
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5

Synthesis of Perovskite Precursors

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Formamidinium iodide (H2N=CHNH2I; FAI) and methylammonium bromide (CH3NH3Br; MABr) were synthesized according to the reported methods31 , and dried in a vacuum oven at 50 °C for 48 h. Lead iodide (PbI2, 99.999%), lead bromide (PbBr2, 99.999%), dimethyl sulfoxide (DMSO, ≥99.9%) and other materials were purchased from Sigma-Aldrich and used as received.
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6

Perovskite Solar Cell Fabrication

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Cesium iodide (CsI) (99.999%, Sigma-Aldrich), lead iodide (PbI2) (99.999%, Sigma-Aldrich) methyl ammonium bromide (Greatcellsolar), formamidinium iodide (Greatcellsolar), tin chloride dihydrate (SnCl2·2H2O), (99.99%, Sigma-Aldrich), 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9′-spirobifluorene (spiro-OMeTAD) (99% Lumtec), lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI, Sigma-Aldrich), 4-tert-butylpyridine (TBP) (96%, Sigma-Aldrich), chlorobenzene (99.9%, spectrophotometric grade) and dimethyl sulfoxide (DMSO) (99.7%, Sigma-Aldrich), N,N-dimethylformamide (DMF) (99.8%, Sigma-Aldrich), anhydrous ethanol, FTO glass substrates, respectively.
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7

Synthetic Procedures for Organic Compounds

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3-aminopyrazole, 3-amino-5-phenylpyrazole, 9H-carbazole, ethyl phenylpropiolate, 4,4-dimethoxydiphenylamine, 1,3-diphenyl-1,3-propanedione, ethyl benzoylacetate, tri-tert-butylphosphine (P(t-Bu)3), palladium acetate (Pd(OAc)2), bis(pinacoloto)diboron, 1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Pd(dppf)Cl2), sodium hydride (NaH), N-bromosuccinimide (NBS), phosphorus(V) oxychloride (POCl3), benzyl bromide, potassium iodate (KIO3), sodium carbonate (Na2CO3), potassium iodide (KI), potassium tert-butoxide (t-BuOK), 1,4-dibromobenzene, N,N-dimethylaniline, potassium phosphate tribasic (K3PO4), copper(I) iodide (CuI), trans-1,2-diaminecyclohexane, potassium acetate (KoAC), Spiro-OMeTAD, formamidinium iodide (FAI), cesium iodide (CsI), lead iodide (PbI2), lead bromide (PbBr2), N,N-dimethylformamide (DMF), tin(IV) oxide (SnO2), magnesium sulfate (MgSO4), tetraethylammonium tetrafluoroborate (Et4NBF4), ferrocene, silica gel (SiO2), dichloromethane (DCM), chloroform (CHCl3), acetic acid (AcOH), dimethyl sulfoxide (DMSO), 1,4-dioxane, tetrahydrofuran (THF), toluene and ethanol (EtOH) were purchased from Sigma-Aldrich, Alfa Aesar or Fluorochem and used as received without any further purification.
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8

Synthesis of Perovskite Materials

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Lead (II) bromide (PbBr2, 99.99%), Lead (II) iodide (PbI2, 99.99%), and Iron (III) chloride anhydrous (FeCl3, 98%) were purchased from Alfa Aesar. Cobalt (II) acetylacetonate (Co(C5H7O2)2, 99%), Octadecene (ODE, 90%), and titanium chloride (TiCl4, 99.9%) were obtained from AcrosOrganics. Oleylamine (OAm, 70%), Oleic acid (OAc, 90%), Methylammonium bromide (MABr), Formamidinium Iodide (FAI), Ni‐(NO3)2·6H2O (98%), C2H2O4·2H2O (99.5%), NaOH (96%), Dimethylformanmide (DMF, extra dry, 99%), Dimethyl sulfoxide (DMSO, extra dry, 99%), 1, 2‐diChlorobenzene (DCB, extra dry, > 98%), Chlorobenzene (CB, extra dry, 99.8%), Isopropanol (extra dry, 99.8%), and other chemicals were purchased from Sigma‐Aldrich.
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9

Perovskite Materials Synthesis and Characterization

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Methylammonium bromide (MABr, 99.9%, Dyesol), methylammonium iodide (MAI, 99.9%, Dyesol), formamidinium bromide (FABr, 99.9%, Dyesol), formamidinium iodide (FAI, 99.9%, Dyesol), cesium bromide (CsBr, Sigma-Aldrich, 99%, metals basis), lead(ii) bromide (PbBr2, Sigma-Aldrich, 99%, metals basis), lead(ii) iodide (PbI2, Sigma-Aldrich, 99%, metals basis), octylamine (Aladdin, 99.5%), oleic acid (Aladdin, 99.5%), hexane (Sigma-Aldrich, 95%), toluene (Sigma-Aldrich, anhydrous, 99.8%), chlorobenzene (Sigma-Aldrich, 99.9%).
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10

Perovskite Solar Cell Fabrication

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Lead bromide (PbBr2, 99%), cesium iodide (CsI, 99%), methylammonium iodide (MAI, 99%), formamidinium iodide (FAI, >98%), 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifuorene (spiro-OMETAD, Sigma-Aldrich, 99%), lithium bis(trifluoromethane)sulfonimide (Li-TFSI, 99%), 4-tert-butylpyridine (TBP, 99%), and tris (2-(1H-pyrazol-1-1yl)-4-tert-butylpyridine) cobalt(iii) tri[bis(trifluoromethane)sulfonamide] (Co(iii) TFSI > 99.95%) were purchased from Sigma-Aldrich. Lead iodide (PbI2, 99.99%) was purchased from Acros. Liquid detergent (Hellmanex) and titanium(iv) chloride (TiCl4) were purchased from Alfa Aesar. Fluorine-doped tin oxide (FTO) glass substrates (sheet resistance: 12–15 Ω per sq.) were purchased from MSE supplies.
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