Abstract
The unique and promising properties of semiconducting organometal halide perovskites have brought these materials to the forefront of solar energy research. Here, we present new insights into the excited-state properties of CH3NH3PbI3 thin films through femtosecond transient absorption spectroscopy measurements. The photoinduced bleach recovery at 760 nm reveals that band-edge recombination follows second-order kinetics, indicating that the dominant relaxation pathway is via recombination of free electrons and holes. Additionally, charge accumulation in the perovskite films leads to an increase in the intrinsic bandgap that follows the Burstein–Moss band filling model. Both the recombination mechanism and the band-edge shift are studied as a function of the photogenerated carrier density and serve to elucidate the behaviour of charge carriers in hybrid perovskites. These results offer insights into the intrinsic photophysics of semiconducting organometal halide perovskites with direct implications for photovoltaic and optoelectronic applications.
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References
Mitzi, D. B., Feild, C. A., Schlesinger, Z. & Laibowitz, R. B. Transport, optical, and magnetic properties of the conducting halide perovskite CH3NH3SnI3 . J. Solid State Chem. 114, 159–163 10.1038/nature12340(1995).
Kagan, C. R., Mitzi, D. B. & Dimitrakopoulos, C. D. Organic–inorganic hybrid materials as semiconducting channels in thin-film field-effect transistors. Science 286, 945–947 (1999).
Mitzi, D. B., Chondroudis, K. & Kagan, C. R. Design, structure, and optical properties of organic–inorganic perovskites containing an oligothiophene chromophore. Inorg. Chem. 38, 6246–6256 (1999).
Hattori, T., Taira, T., Era, M., Tsutsui, T. & Saito, S. Highly efficient electroluminescence from a heterostructure device combined with emissive layered-perovskite and an electron-transporting organic compound. Chem. Phys. Lett. 254, 103–108 (1996).
Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009).
Etgar, L. et al. Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells. J. Am. Chem. Soc. 134, 17396–17399 (2012).
Kim, H.-S. et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci. Rep. 2, 591 (2012).
Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N. & Snaith, H. J. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643–647 (2012).
Im, J.-H., Lee, C.-R., Lee, J.-W., Park, S.-W. & Park, N.-G. 6.5% efficient perovskite quantum-dot-sensitized solar cell. Nanoscale 3, 4088–4093 (2011).
Christians, J. A., Fung, R. C. M. & Kamat, P. V. An inorganic hole conductor for organo-lead halide perovskite solar cells. Improved hole conductivity with copper iodide. J. Am. Chem. Soc. 136, 758–764 (2014).
Stoumpos, C. C., Malliakas, C. D. & Kanatzidis, M. G. Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorg. Chem. 52, 9019–9038 (2013).
Xing, G. et al. Long-range balanced electron- and hole-transport lengths in organic–inorganic CH3NH3PbI3 . Science 342, 344–347 (2013).
Stranks, S. D. et al. Electron–hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).
Liang, K., Mitzi, D. B. & Prikas, M. T. Synthesis and characterization of organic–inorganic perovskite thin films prepared using a versatile two-step dipping technique. Chem. Mater. 10, 403–411 (1998).
Burschka, J. et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316–319 (2013).
Hodes, G. Perovskite-based solar cells. Science 342, 317–318 (2013).
Park, N. Organometal perovskite light absorbers toward a 20% efficiency low-cost solid-state mesoscopic solar cell. J. Phys. Chem. Lett. 4, 2423–2429 (2013).
Liu, M., Johnston, M. B. & Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395–398 (2013).
Docampo, P., Ball, J. M., Darwich, M., Eperon, G. E. & Snaith, H. J. Efficient organometal trihalide perovskite planar-heterojunction solar cells on flexible polymer substrates. Nature Commun. 4, 2761 (2013).
Heo, J. H. et al. Efficient inorganic–organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors. Nature Photon. 7, 486–491 (2013).
Snaith, H. J. Perovskites: the emergence of a new era for low-cost, high-efficiency solar cells. J. Phys. Chem. Lett. 4, 3623–3630 (2013).
Tvrdy, K., Frantsuzov, P. A. & Kamat, P. V. Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles. Proc. Natl Acad. Sci. USA 108, 29–34 (2011).
Abrusci, A. et al. High-performance perovskite–polymer hybrid solar cells via electronic coupling with fullerene monolayers. Nano Lett. 13, 3124–3128 (2013).
Zhao, Y. & Zhu, K. Charge transport and recombination in perovskite (CH3NH3)PbI3 sensitized TiO2 solar cells. J. Phys. Chem. Lett. 4, 2880–2884 (2013).
Christians, J. A., Leighton, D. T. & Kamat, P. V. Rate limiting interfacial hole transfer in Sb2S3 solid-state solar cells. Energy Environ. Sci. 7, 1148–1158 (2014).
Ghanassi, M. et al. Time-resolved measurements of carrier recombination in experimental semiconductor-doped glasses: confirmation of the role of Auger recombination. Appl. Phys. Lett. 62, 78 (1993).
Robel, I., Bunker, B. A., Kamat, P. V & Kuno, M. Exciton recombination dynamics in CdSe nanowires: bimolecular to three-carrier Auger kinetics. Nano Lett. 6, 1344–1349 (2006).
Wehrenfennig, C., Eperon, G. E., Johnston, M. B., Snaith, H. J. & Herz, L. M. High charge carrier mobilities and lifetimes in organolead trihalide perovskites. Adv. Mater. 26, 1584–1589 (2014).
Xing, G. et al. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nature Mater. 13, 476–480 (2014).
Deschler, F. et al. High photoluminescence efficiency and optically-pumped lasing in solution-processed mixed halide perovskite semiconductors. J. Phys. Chem. Lett. 5, 1421–1426 (2014).
Marchioro, A. et al. Unravelling the mechanism of photoinduced charge transfer processes in lead iodide perovskite solar cells. Nature Photon. 8, 250–255 (2014).
Burstein, E. Anomalous optical absorption limit in InSb. Phys. Rev. 93, 632–633 (1954).
Moss, T. S. The interpretation of the properties of indium antimonide. Proc. Phys. Soc. B 67, 775–782 (1954).
Kamat, P. V., Dimitrijevic, N. M. & Nozik, A. J. Dynamic Burstein–Moss shift in semiconductor colloids. J. Phys. Chem. 93, 2873–2875 (1989).
Kawamura, K., Maekawa, K., Yanagi, H., Hirano, M. & Hosono, H. Observation of carrier dynamics in CdO thin films by excitation with femtosecond laser pulse. Thin Solid Films 445, 182–185 (2003).
Hickey, S. G., Riley, D. J. & Tull, E. J. Photoelectrochemical studies of CdS nanoparticle modified electrodes: absorption and photocurrent investigations. J. Phys. Chem. B 104, 7623–7626 (2000).
Muñoz, M. et al. Burstein–Moss shift of n-doped In0.53Ga0.47As/InP. Phys. Rev. B 63, 233302 (2001).
Giorgi, G., Fujisawa, J., Segawa, H. & Yamashita, K. Small photocarrier effective masses featuring ambipolar transport in methylammonium lead iodide perovskite: a density functional analysis. J. Phys. Chem. Lett. 4, 4213–4216 (2013).
Vodopyanov, K., Graener, H., Phillips, C. & Tate, T. Picosecond carrier dynamics and studies of Auger recombination processes in indium arsenide at room temperature. Phys. Rev. B 46, 13194–13200 (1992).
Tanaka, K. et al. Comparative study on the excitons in lead-halide-based perovskite-type crystals CH3NH3PbBr3 CH3NH3PbI3 . Solid State Commun. 127, 619–623 (2003).
Hamberg, I. & Granqvist, C. G. Evaporated Sn-doped In2O3 films: basic optical properties and applications to energy-efficient windows. J. Appl. Phys. 60, R123 (1986).
Kim, H.-S. et al. Mechanism of carrier accumulation in perovskite thin-absorber solar cells. Nature Commun. 4, 2242 10.1038/ncomms3242(2013).
Hirasawa, M., Ishihara, T., Goto, T., Uchida, K. & Miura, N. Magnetoabsorption of the lowest exciton in perovskite-type compound (CH3NH3)PbI3 . Phys. B Condens. Matter 201, 427–430 (1994).
Sun, S. et al. The origin of high efficiency in low-temperature solution-processable bilayer organometal halide hybrid solar cells. Energy Environ. Sci. 7, 399–407 (2014).
Amo, A., Martín, M., Viña, L., Toropov, A. & Zhuravlev, K. Interplay of exciton and electron–hole plasma recombination on the photoluminescence dynamics in bulk GaAs. Phys. Rev. B 73, 035205 (2006).
Burstein, E. Exciton-polaritons in nonlinear optical phenomena in semiconductors: an overview of major developments. Phys. Rep. 194, 253–272 (1990).
Gay, J. Screening of excitons in semiconductors. Phys. Rev. B 4, 2567–2575 (1971).
Schweizer, H. et al. Ionization of the direct-gap exciton in photoexcited germanium. Phys. Rev. Lett. 51, 698–701 (1983).
Li, X. D., Chen, T. P., Liu, P., Liu, Y. & Leong, K. C. Effects of free electrons and quantum confinement in ultrathin ZnO films: a comparison between undoped and Al-doped ZnO. Opt. Express 21, 14131–14138 (2013).
Thomas, G. A. & Rice, T. M. Trions, molecules and excitons above the Mott density in Ge. Solid State Commun. 23, 359–363 (1977).
Acknowledgements
The authors thank J. Christians for his input on perovskite film preparation and discussion of experimental outcomes. The authors thank G. Hartland and M. Kuno for their commentary and interpretation of experimental results. The authors acknowledge the Center for Sustainable Energy at Notre Dame (cSEND) Materials Characterization Facilities for the use of the Bruker DektakXT profilometer. The research described herein was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US Department of Energy (award DE-FC02-04ER15533). This is contribution number NDRL No. 5004 from the Notre Dame Radiation Laboratory.
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J.S.M. and P.V.K. conceived the original experimental ideas and details. J.S.M. carried out all aspects of film preparation and optical measurements. J.S.M. prepared the figures and wrote the initial draft. Both authors contributed to the discussion, analysis and writing of the final paper.
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Manser, J., Kamat, P. Band filling with free charge carriers in organometal halide perovskites. Nature Photon 8, 737–743 (2014). https://doi.org/10.1038/nphoton.2014.171
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DOI: https://doi.org/10.1038/nphoton.2014.171
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