Ternary Halide Perovskites for Highly Efficient Solution
Supporting Information for:
Ternary Halide Perovskites for Highly Efficient Solution-Processed Hybrid Solar Cells Jaeki Jeong†, Hak-Beom Kim†, Haeyeon Kim†, Bright Walker†, Seyeong Song†, Jungwoo Heo‡, Yung Jin Yoon†, Yimhyun Jo¶, Hyosung Choi Ψ, Gi-Hwan Kim†, Dong Suk Kim¶,* and Jin Young Kim†,** † Department of Energy Engineering, ‡Department of Physics and Applied Mathematics, Ulsan National Institute of Science and Technology (UNIST) and ¶KIER-UNIST Advanced Center for Energy, Korea Institute of Energy Research (KIER), 50 UNIST-gil, Ulju-gun, Ulsan 44919, South Korea. Ψ
Research Institute for Convergence of Basic Sciences, Department of Chemistry and Institute for
Materials Design, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul, South Korea. AUTHOR INFORMATION Corresponding Author **E-mail: [email protected]; Fax: +82-52-217-2909; Tel: +82- 52-217-2911 *E-mail: [email protected]; Fax: +82-52-217-2579; Tel: +82- 52-217-2942
1
Experimental Section Materials and preparation of perovskite: lead chloride (PbCl2), lead bromide (PbBr2), anhydrous dimethylacetamide (DMA) and anhydrous N,N-dimethylformamide (DMF) were purchased from Sigma-Aldrich and were used without purification. Methylammonium iodide (MAI) was prepared by mixing 30 ml CH3NH2 (40 wt% in water, Sigma Aldrich) and 30 ml HI (57 wt% in water, Sigma Aldrich) in a 250 ml, three-neck flask at 0 precipitate was recovered by evaporation under vacuum at 60
for 2 hr with stirring. The
for 1h. To purify, the MAI
precursor was re-dissolved in ethanol and recrystallized from diethyl either. Finally, the MAI product was dried at 60
under vacuum oven for 24 hr. To prepare MAPbI3-xClx precursor
solutions, MAI and PbCl2 were dissolved at a 3:1 molar ratio in a mixture of DMA and DMF solution (9:1 [v/v]) with a concentration of 40 wt%. For the ternary halide MAPbI3-x-y BryClx precursor solution, MAI, PbCl2 and PbBr2 were dissolved at a 3 : 1-y : y molar ratio in same mixed solution at 40 wt% concentration. The obtained solution was stirred at room temperature for 2 hr in air. Scanning electron microscope measurements (SEM) were performed using an S-4800 Hitachi high-Technology microscope. SEM samples were prepared by coating perovskite presursor solutions onto glass substrates by spin-coating at 5000 rpm, followed by post annealing at 90 °C for 90 min on a hotplate. For X-ray diffraction (XRD) measurements, perovskite films were coated on PEDOT:PSS-coated glass substrates and diffractorams were collected using a Bruker, D8 ADVANCE diffractometer at a scan rate of 2.4° min-1. UV-vis absorption was measured using a Varian Cary 5000 spectrophotometer. AFM images were obtained using a Veeco Multimode AFM microscope in a tapping mode.
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Device fabrication and characterization: FTO-coated glass substrates were cleaned by ultrasonication in deionized water, acetone and isopropyl alcohol for 10 min each. A poly(3,4ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) layer was deposited on cleaned FTO substrates by spin-casting at 3000 rpm for 40s, followed by annealing at 150 °C for 15 min. On top of PEDOT:PSS (AI4083) layer, binary and tenary halide perovskite precursor solutions were spin-cast at 5000 rpm for 30 s and dried on a hot-plate at 90 °C for 90 min in air atmosphere. On top of the perovskite layer, a 25 mg/ml solution of PC61BM in 1:1 mixture of chlorobenzene and chloroform was spin-cast at 900 rpm. Subsequently, an Al electrode with a thickness of 100 nm was deposited on the PC61BM layer under vacuum (
Ternary Halide Perovskites for Highly Efficient Solution-Processed Hybrid Solar Cells Jaeki Jeong†, Hak-Beom Kim†, Haeyeon Kim†, Bright Walker†, Seyeong Song†, Jungwoo Heo‡, Yung Jin Yoon†, Yimhyun Jo¶, Hyosung Choi Ψ, Gi-Hwan Kim†, Dong Suk Kim¶,* and Jin Young Kim†,** † Department of Energy Engineering, ‡Department of Physics and Applied Mathematics, Ulsan National Institute of Science and Technology (UNIST) and ¶KIER-UNIST Advanced Center for Energy, Korea Institute of Energy Research (KIER), 50 UNIST-gil, Ulju-gun, Ulsan 44919, South Korea. Ψ
Research Institute for Convergence of Basic Sciences, Department of Chemistry and Institute for
Materials Design, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul, South Korea. AUTHOR INFORMATION Corresponding Author **E-mail: [email protected]; Fax: +82-52-217-2909; Tel: +82- 52-217-2911 *E-mail: [email protected]; Fax: +82-52-217-2579; Tel: +82- 52-217-2942
1
Experimental Section Materials and preparation of perovskite: lead chloride (PbCl2), lead bromide (PbBr2), anhydrous dimethylacetamide (DMA) and anhydrous N,N-dimethylformamide (DMF) were purchased from Sigma-Aldrich and were used without purification. Methylammonium iodide (MAI) was prepared by mixing 30 ml CH3NH2 (40 wt% in water, Sigma Aldrich) and 30 ml HI (57 wt% in water, Sigma Aldrich) in a 250 ml, three-neck flask at 0 precipitate was recovered by evaporation under vacuum at 60
for 2 hr with stirring. The
for 1h. To purify, the MAI
precursor was re-dissolved in ethanol and recrystallized from diethyl either. Finally, the MAI product was dried at 60
under vacuum oven for 24 hr. To prepare MAPbI3-xClx precursor
solutions, MAI and PbCl2 were dissolved at a 3:1 molar ratio in a mixture of DMA and DMF solution (9:1 [v/v]) with a concentration of 40 wt%. For the ternary halide MAPbI3-x-y BryClx precursor solution, MAI, PbCl2 and PbBr2 were dissolved at a 3 : 1-y : y molar ratio in same mixed solution at 40 wt% concentration. The obtained solution was stirred at room temperature for 2 hr in air. Scanning electron microscope measurements (SEM) were performed using an S-4800 Hitachi high-Technology microscope. SEM samples were prepared by coating perovskite presursor solutions onto glass substrates by spin-coating at 5000 rpm, followed by post annealing at 90 °C for 90 min on a hotplate. For X-ray diffraction (XRD) measurements, perovskite films were coated on PEDOT:PSS-coated glass substrates and diffractorams were collected using a Bruker, D8 ADVANCE diffractometer at a scan rate of 2.4° min-1. UV-vis absorption was measured using a Varian Cary 5000 spectrophotometer. AFM images were obtained using a Veeco Multimode AFM microscope in a tapping mode.
2
Device fabrication and characterization: FTO-coated glass substrates were cleaned by ultrasonication in deionized water, acetone and isopropyl alcohol for 10 min each. A poly(3,4ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) layer was deposited on cleaned FTO substrates by spin-casting at 3000 rpm for 40s, followed by annealing at 150 °C for 15 min. On top of PEDOT:PSS (AI4083) layer, binary and tenary halide perovskite precursor solutions were spin-cast at 5000 rpm for 30 s and dried on a hot-plate at 90 °C for 90 min in air atmosphere. On top of the perovskite layer, a 25 mg/ml solution of PC61BM in 1:1 mixture of chlorobenzene and chloroform was spin-cast at 900 rpm. Subsequently, an Al electrode with a thickness of 100 nm was deposited on the PC61BM layer under vacuum (
