Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials
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1 Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials L. Ciammaruchi, R. K. Misra, S. Aharon, D. Mogilyansky, L. Etgar, I. Visoly-Fisher and E. A. Katz 20 th Sede Boqer Symposium on Solar Electricity Production September 26-28, 2016 BGU-ENEA WORKSHOP
2 Motivation: fig Development of Mixed Halide Perovskite-based PV materials MAPbI n Br 3 n combining rte high efficiency* operational stability** Research question: digghfghfgh How is operational stability dependent on the halide content in MAPbX 3? * Kojima et al., J. Am. Chem. Soc., 2009, 131 (17), pp ** R. K. Misra, I. Visoly-Fisher, E. A. Katz, et al., J. Phys. Chem. Lett., 2015, 6 (3), pp
3 Pure Halide Perovskite PV Materials MAPbX 3 Solar absorption Stability* * 100 suns + T 50 C X = I X = Br Mixed Halide MAPb(I 1-x Br x ) 3 * R. K. Misra, I. Visoly-Fisher, E. A. Katz, et al., J. Phys. Chem. Lett., 2015, 6 (3), pp
4 Mixed halide MAPb(I 1-x Br x ) 3 Perovskite PV Materials si si Stability si Seok et al., Nano Lett., 2013, 13 (4), pp 1764
5 R. K. Misra, L. Ciammaruchi et al., ChemSusChem 2016, 9, 1 7 Experiment layout Accelerated testing 100 sun+t 50 C Encapsulated Films MAPb(I 1-x Br x ) 3 various compositions Seq. dep. method Comparison to degradation under outdoor 1sun exposure (validate acc. testing) MAPbI 3 - MAPbBr 3 more stable than mixed halides MAPb(I 1-x Br x ) 3
6 Assessment Validation Usage of Accelerated Stability Tests for PV Materials/Cells 1. Gordon, J. M.; Katz, E. A.; Feuermann, D.; Huleihil, M. Toward Ultra-High-Flux Photovoltaic Concentration. Appl. Phys. Lett. 2004, 84, Tromholt, T.; Katz, E. A.; Hirsch, B.; Vossier, A.; Krebs, F. C. Effects of Concentrated Sunlight on Organic Photovoltaics. Appl. Phys. Lett. 2010, 96, I. Visoly-Fisher, E.A. Katz, et al., Sol. Ener. Mater. & Sol. Cells 134 (2015), L. Ciammaruchi, F. Brunetti, I. Visoly-Fisher, Solvent effects on the morphology and stability of PTB7:PCBM based solar cells, Solar Energy 137 (2016),
![Encapsulated Films MAPb(I 1-x Br x ) 3 various compositions Characterization: UV/Vis XRD [a] [b] [c] [d] [e] X=1 X=0.](/docs-images/80/80463980/images/7-2.jpg "16 [a]: Ratio in the organic precursor solution [b]: peaks full width at half maximum (FWHM) [c]: Br content according to the precursor materials [d]: Br content calculated from the XRD (Vegard s")
7 Encapsulated Films MAPb(I 1-x Br x ) 3 various compositions Characterization: UV/Vis XRD [a] [b] [c] [d] [e] X=1 X=0.16 [a]: Ratio in the organic precursor solution [b]: peaks full width at half maximum (FWHM) [c]: Br content according to the precursor materials [d]: Br content calculated from the XRD (Vegard s law) [e]: optical bandgap determined from UV/Vis spectrum X=0 R. K. Misra, L. Ciammaruchi et al., ChemSusChem 2016, 9, 1 7
8 Results - MAPb(I 1-x Br x ) 3 - XRD As fabricated After 100sun*hr exposure X=1 X=0.16 X=0 PbI2 X=1 X=0.16 X=0 Intensity [arb.units] PbI 2 Sample 3 c Exposed PbI 2 Sample 4 d Exposed Nonexposed Nonexposed [degrees] [degrees]
9 Results - MAPb(I 1-x Br x ) 3 - XRD + UV/Vis Intensity [arb.units] PbI 2 Sample 3 c Exposed PbI 2 Sample 4 d Exposed Nonexposed Nonexposed [degrees] [degrees]
10 Results - MAPb(I 1-x Br x ) 3 - UV/Vis 100 sun exposure X=1 ADS = # absorbed#photons#by #exposed#film# # absorbed#photons#by pristine#film mg173/astmg173.html X=0.16 X=1 X=0 100 sun - pvsk abs. range only X=1 X=0 1 sun exposure
11 Results - MAPb(I 1-x Br x ) 3 XRD + UV/Vis # ADS = # abs. photons#by #exposed#film# # abs. photons#by pristine#film Correlation between increased FWHM (mixed halide) and enhanced absoption degradation
12 Suggested degradation mechanisms: Perovskite decomposition proceeding via PbI 2 formation and perovskite Br-enrichment Connection between enhanced decomposition rate and smaller crystal coherence length (FWHM). Possible explanation includes: o distortion of the skeletal octahedral structure of [PbI 6 ]4 - o corresponding perovskite strain amplification Excess Br - grain size - binding energy -traps formation* * ( stolen from prof. Lanzani yesterday s talk) R. K. Misra, L. Ciammaruchi et al., ChemSusChem 2016, 9, 1 7
13 Conclusions: Perovskite stability: MAPbBr 3 > MAPbI 3 > MAPb(I 1-x Br x ) 3 Photolysis induced/accelerated by a combined effect of light and heat, resulting in perovskite decomposition (PbI 2 and organics). Perovskites with a smaller structural defect concentration more stable to photolysis. Crystal coherence length as an indicator for relative photolysis degradation rate. R. K. Misra, L. Ciammaruchi et al., ChemSusChem 2016, 9, 1 7
14 Acknowledgments: Thank you for your attention!
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