2 methoxyethanol

Nickel (II) nitrate hexahydrate (Ni(NO₃)₂ • 6H₂O), trioctylphosphine (TOP, 97%), titanium (IV) tetraisopropoxide (TTIP, >98%), 2-methoxyethanol (CH₃OCH₂CH₂OH, ≥99.5%), lithium perchlorate (LiClO₄, ≥98.0%), ethanol (EtOH, 99.5%) and isopropyl alcohol (IPA, 99.5%) were purchased from Sigma-Aldrich (St. Louis, MO, USA). Iodine (I₂, synthetic grade), lithium iodide (LiI, synthetic grade), and poly(ethylene glycol) (PEG, MW~20,000) were supplied by Merck (Rahway, NJ, USA). Acetone ( $\ge$ 99%), 4-tert-butylpyridine (tBP, 96%), and tert-butyl alcohol (tBA, 96%) were acquired from Acros, and 3-methoxypropionitrile (MPN, 99%) was bought from Fluka (Buchs, Switzerland). Transparent titanium dioxide (TiO₂) paste (TL paste, Ti-nanoxide HT/SP, 13 nm), cis-diisothiocyanato-bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium (II) bis(tetrabutylammonium) (N719 dye), and 1,2-dimethyl-3-propylimidazolium iodide (DMPII) were obtained from Solaronix (S.A., Aubonne, Switzerland). Commercial light-scattering TiO₂ particles (ST-41 with 200 nm) were procured from Ishihara Sangyo, Ltd. (Nishi-ku, Osaka, Japan). Nitric acid (HNO₃, 65% solution in water), acetonitrile (ACN, 99.99%) was received from J. T. Baker. Polyester tape (1350F-1, 63 μm) was from the 3M Company (St. Paul, MN, USA).

Cesium iodide (CsI, > 99.9%), formamidinium iodide (FAI, > 99.5%), methylammonium iodide (MAI, > 99.5%), lead(II) iodide (PbI₂, > 99.99%), lead(II) bromide (PbBr₂, > 99.99%), bathocuproine (BCP), and [6, 6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) were purchased from Xi’an Polymer Light Technology. Tin(II) iodide (SnI₂, 99.99%), tin(II) fluoride (SnF₂, 99%), nickel(II) nitrate hexahydrate [Ni(NO₃)₂·6H₂O], 2-methoxyethanol, acetylacetone, ammonia, N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.8%), isopropanol (IPA), chlorobenzene (CB), γ-butyrolactone (GBL), and anisole were obtained from Sigma-Aldrich. d-Homoserine lactone hydrochloride (D-HLH) was purchased from Macklin. Poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS, Clevios™ PVP AI 4083) was purchased from Heraues.

Chloramine-T hydrate Ref # 857319, Trans-4-hydroxy-L Proline Ref # 56250, Potassium iodide Ref #60399, Potassium dihydrogen phosphate Ref #4,795488-Dimethylaminobenzaldehyde Ref #156477, Perchloric acid, 70% Ref # 24252 and 2-Methoxyethanol Ref#185469 were from Sigma-Aldrich (Saint Quentin Fallavier, France). LPS was from E. Coli serotype 0127: B8 (Sigma Aldrich), BCG vaccine was purchased from Sanofi Pasteur and composed of 0.5 mg of the Brazilian strain (BCG Biomed-Lublin Laboratory).

A clean FTO was UVO treated for 10 min. The TiO₂ blocking layer (bl-TiO₂) was spin coated on a FTO glass substrate with a titanium(IV) diisopropoxide bis(acetylacetonate) solution diluted in butanol (1:10, v/v) at 700 rpm for 8 sec, 1000 rpm for 10 sec and 2000 rpm for 40 sec followed by dryig at 125 °C for 5 min. Mesoporous titanium oxide (mp-TiO₂) layer was spin coated on the bl-TiO₂ with 1.2 g of TiO₂ nanoparticles (40 nm size from ENB Korea) diluted in 10 ml of anhydrous ethanol solution at a speed of 2000 rpm for 20 sec and finally annealed at 550 °C for 1 hr and the UVO treated for 15 min. The ZnO sol-gel was synthesized by reacting zinc acetate dihydrate (1.6 g, Sigma Aldrich), ethanolamine (0.5 g, Sigma Aldrich) and 2-methoxy-ethanol (10 ml, Sigma Aldrich) and stirr for 4 hrs at room temperature and spin coated over the mp-TiO₂ at 5000 rpm for 40 sec and finally annealed at 300 °C for 1 hr^{33 (link)}. MAPbI₃ layers were fabricated according to the method described above. The Spiro-OMeTAD HTM was deposited via spin-coating at 3000 rpm for 30 s. The solution was prepared by mixing 29 mg of Spiro-OMeTAD, 7 μL of 170 mg/ml Li-TFSI in acetonitrile, and 11 μL of 4-tBPy. Finally, device fabrication was completed by thermal evaporation of the thin MoO₃ layer and thick Ag layer on top of the HTM film under reduced pressure (less than 10⁻⁶ Torr).

PbI₂(99.99%) and PbBr₂ (99.9%) were purchased from TCI. PM6, Y6, and PFN‐Br were purchased from Derthon Optoelectronic Material Science Technology Co., Ltd. SnO₂ (15% in H₂O colloidal dispersion) was purchased from Alfa Aesar. Poly(triarylamine) (PTAA) was purchased from Xi'an Polymer Light Technology Corp. Zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O, 99.995%) and chlorobenzene were purchased from Aladdin. CsI (99.999%), N,N‐Dimethylformamide (DMF), and dimethylsulfoxide (DMSO) were purchased from J & K. Ethanolamine, 2‐Methoxyethanol, and isopropanol were purchased from Sigma–Aldrich.

PTB7-Th (weight-average molecular weight=126 kDa, polydispersity index=2.5) and PC₇₁BM (purity>99%) were purchased from 1-Material (Canada) and Nano-C (USA), respectively. PEOz (weight-average molecular weight=50 kDa, polydispersity index=3–4) was supplied by Sigma-Aldrich (USA) and used without further purification. The PEOz solutions were prepared by varying the concentration up to 8 mg ml⁻¹ in methanol. Binary polymer:fullerene solutions were prepared using chlorobenzene as a solvent in the presence of 1,8-diiodooctane (chlorobenzene:1,8-diiodooctane =97:3 by volume) at a solid concentration of 20 mg ml⁻¹ (PTB7-Th:PC₇₁BM=1:1.5 by weight) and were vigorously stirred at room temperature for 12 h before spin coating. The ZnO precursor solutions were prepared by dissolving zinc acetate dihydrate (Sigma-Aldrich, 1 g) and ethanolamine (Sigma-Aldrich, 0.28 g) in 2-methoxyethanol (Sigma-Aldrich, 10 ml) and stirred at 60 °C for 3 h and then at room temperature for 12 h before spin coating.