Here we report on the material chemistry following crystallization in the presence of water vapor of chlorinated formamidinium lead-triiodide (NH2CH = NH2PbI3−xClx) perovskite films. We found in-situ exposure to water vapor reduces, or possibly eliminates, the retention of chlorine (Cl) inside NH2CH = NH2PbI3−xClx crystals. There is a strong tendency toward Cl volatility, which indicates the sensitivity of these materials for their integration into solar cells. The requisite for additional efforts focused on the mitigation of water vapor is reported. Based on the in situ results, hot casting (<100 °C) in dry conditions demonstrates improved film coverage and Cl retention with efficiencies reaching 12.07%.
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J.L. Sawin and F. Sverrisson: Renewable 2014 Global Status Report (REN21 Secretariat, Paris, France, 2014).
M.A. Green, A. Ho-Baillie, and H.J. Snaith: The emergence of perovskite solar cells. Nat. Photonics 8, 506 (2014).
N.J. Jeon, J.H. Noh, W.S. Yang, Y.C. Kim, S. Ryu, J. Seo, and S.I. Seok: Compositional engineering of perovskite materials for high-performance solar cells. Nature 517, 476 (2015).
M. Gratzel: The light and shade of perovskite solar cells. Nat. Mater. 13, 838 (2014).
N. Pellet, P. Gao, G. Gregori, T.-Y. Yang, M.K. Nazeeruddin, J. Maier, and M. Grätzel: Mixed-organic-cation perovskite photovoltaics for enhanced solar-light harvesting. Angew. Chem. Int. Ed. 53, 3151 (2014).
P.P. Boix, K. Nonomura, N. Mathews, and S.G. Mhaisalkar: Current progress and future perspectives for organic/inorganic perovskite solar cells. Mater. Today 17, 16 (2014).
D.B. Mitzi: Synthesis, Structure, and Properties of Organic-Inorganic Perovskites and Related Materials, in Progress in Inorganic Chemistry (UNEP, Paris, France, 2007), p. 1.
G.E. Eperon, S.D. Stranks, C. Menelaou, M.B. Johnston, L.M. Herz, and H.J. Snaith: Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells. Energy Environ. Sci. 7, 982 (2014).
J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M.K. Nazeeruddin, and M. Gratzel: Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316 (2013).
Y. Zhao and K. Zhu: Efficient planar perovskite solar cells based on 1.8 eV band gap CH3NH3PbI2Br nanosheets via thermal decomposition. J. Am. Chem. Soc. 136, 12241 (2014).
Y. Zhao and K. Zhu: CH3NH3Cl-assisted one-step solution growth of CH3NH3PbI3: structure, charge-carrier dynamics, and photovoltaic properties of perovskite solar cells. J. Phys. Chem. C 118, 9412 (2014).
Q. Chen, H. Zhou, Y. Fang, A.Z. Stieg, T.-B. Song, H.-H. Wang, X. Xu, Y. Liu, S. Lu, J. You, P. Sun, J. McKay, M.S. Goorsky, and Y. Yang: The optoelectronic role of chlorine in CH3NH3PbI3(Cl)-based perovskite solar cells. Nat. Commun. 6, 1, 7269 (2015).
E.T. Hoke, D.J. Slotcavage, E.R. Dohner, A.R. Bowring, H.I. Karunadasa, and M.D. McGehee: Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics. Chem. Sci. 6, 613 (2015).
A. Mei, X. Li, L. Liu, Z. Ku, T. Liu, Y. Rong, M. Xu, M. Hu, J. Chen, Y. Yang, M. Grätzel, and H. Han: A hole-conductor-free, fully printable mesoscopic perovskite solar cell with high stability. Science 345, 295 (2014).
G. Niu, W. Li, F. Meng, L. Wang, H. Dong, and Y. Qiu: Study on the stability of CH3NH3PbI3 films and the effect of post-modification by aluminum oxide in all-solid-state hybrid solar cells. J. Mater. Chem. A 2, 705 (2014).
J. You, Y. Yang, Z. Hong, T.-B. Song, L. Meng, Y. Liu, C. Jiang, H. Zhou, W.-H. Chang, G. Li, and Y. Yang: Moisture assisted perovskite film growth for high performance solar cells. Appl. Phys. Lett. 105, 183902 (2014).
J.A. Christians, P.A. Miranda Herrera, and P.V. Kamat: Transformation of the excited state and photovoltaic efficiency of CH3NH3PbI3 perovskite upon controlled exposure to humidified air. J. Am. Chem. Soc. 137, 1530 (2015).
F. Wang, H. Yu, H. Xu, and N. Zhao: HPbI3: a new precursor compound for highly efficient solution-processed perovskite solar cells. Adv. Funct. Mater. 25, 1120 (2015).
S. Lv, S. Pang, Y. Zhou, N.P. Padture, H. Hu, L. Wang, X. Zhou, H. Zhu, L. Zhang, C. Huang, and G. Cui: One-step, solution-processed formamidinium lead trihalide (FAPbI(3-x)Clx) for mesoscopic perovskite-polymer solar cells. Phys. Chem. Chem. Phys. 16, 19206 (2014).
E.L. Unger, A.R. Bowring, C.J. Tassone, V. Pool, A. Gold-Parker, R. Cheacharoen, K.H. Stone, E.T. Hoke, M.F. Toney, and M.D. McGehee: Chloride in lead chloride-derived organo-metal halides for perovskite-absorber solar cells. Chem. Mater. 26, 7158–7165 (2014).
G. Niu, X. Guo, and L. Wang: Review of recent progress in chemical stability of perovskite solar cells. J. Mater. Chem. A 3, 8970–8980 (2015).
T.W. Hansen, J.B. Wagner, P.L. Hansen, S. Dahl, H. Topsøe, and C.J.H. Jacobsen: Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst. Science 294, 1508 (2001).
D. Alsem, N.J. Salmon, R.R. Unocic, G.M. Veith, and K.L. More: in-situ liquid and gas transmission electron microscopy of nano-scale materials. Microsc. Microanal. 18(Supplement S2), 1158 (2012).
J.A. Aguiar, S. Wozny, T.G. Holesinger, T. Aoki, M.K. Patel, M. Yang, J.J. Berry, M. Al-Jassim, W. Zhou, and K. Zhu: In situ investigation of the formation and metastability of formamidinium lead tri-iodide perovskite solar cells. Energy Environ. Sci. 9, 2372 (2016).
J.A. Aguiar, S. Wozny, T.G. Holesinger, T. Aoki, M.K. Patel, M. Yang, J.J. Berry, M. Al-Jassim, W. Zhou, and K. Zhu: In situ investigation of the role of temperature on the formation and metastability of higher efficiency perovskite solar cells. Energy Environ. Sci. 9, 2372–2382 (2016).
R. Senga and K. Suenaga: Single-atom electron energy loss spectroscopy of light elements. Nat. Commun. 6, 7943 (2015).
R.F. Egerton, P. Li, and M. Malac: Radiation damage in the TEM and SEM. Micron 35, 399 (2004).
G. Grancini, S. Marras, M. Prato, C. Giannini, C. Quarti, F. De Angelis, M. De Bastiani, G.E. Eperon, H.J. Snaith, L. Manna, and A. Petrozza: The impact of the crystallization processes on the structural and optical properties of hybrid perovskite films for photovoltaics. J. Phys. Chem. Lett. 5, 3836 (2014).
D.E. Starr, G. Sadoughi, E. Handick, R.G. Wilks, J.H. Alsmeier, L. Kohler, M. Gorgoi, H.J. Snaith, and M. Bar: Direct observation of an inhomogeneous chlorine distribution in CH3NH3PbI3−xClx layers: surface depletion and interface enrichment. Energy Environ. Sci. 8, 1609 (2015).
W. Nie, H. Tsai, R. Asadpour, J.-C. Blancon, A.J. Neukirch, G. Gupta, J.J. Crochet, M. Chhowalla, S. Tretiak, M.A. Alam, H.-L. Wang, and A.D. Mohite: High-efficiency solution-processed perovskite solar cells with millimeter-scale grains. Science 347, 522 (2015).
This work was supported by the National Renewable Energy Laboratory as a part of the Non-Proprietary Partnering Program under Contract No. DE-AC36-08-GO28308 within the U.S. Department of Energy. TGH and the hot-stage in situ STEM work were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences, and Engineering Division under grant number 2013LANL8400.
The supplementary material for this article can be found at https://doi.org/10.1557/mrc.2017.52
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Aguiar, J.A., Alkurd, N.R., Wozny, S. et al. In situ investigation of halide incorporation into perovskite solar cells. MRS Communications 7, 575–582 (2017). https://doi.org/10.1557/mrc.2017.52