Abstract
Organic–inorganic hybrid perovskite materials are emerging as highly attractive semiconductors for use in optoelectronics. In addition to their use in photovoltaics, perovskites are promising for realizing light-emitting diodes (LEDs) due to their high colour purity, low non-radiative recombination rates and tunable bandgap. Here, we report highly efficient perovskite LEDs enabled through the formation of self-assembled, nanometre-sized crystallites. Large-group ammonium halides added to the perovskite precursor solution act as a surfactant that dramatically constrains the growth of 3D perovskite grains during film forming, producing crystallites with dimensions as small as 10 nm and film roughness of less than 1 nm. Coating these nanometre-sized perovskite grains with longer-chain organic cations yields highly efficient emitters, resulting in LEDs that operate with external quantum efficiencies of 10.4% for the methylammonium lead iodide system and 9.3% for the methylammonium lead bromide system, with significantly improved shelf and operational stability.
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References
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. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nat. Mater. 13, 476–480 (2014).
Miyata, A. et al. Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites. Nat. Phys. 11, 582–587 (2015).
Noriko, O.-Y., Takasuke, M. & Hiroshi, S. Dielectric study of CH3NH3PbX3 (X = Cl, Br, I). J. Phys. Chem. Solids 53, 935–939 (1992).
Yin, W.-J., Shi, T. & Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl. Phys. Lett. 104, 063903 (2014).
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).
Burschka, J. et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316–319 (2013).
Liu, M., Johnston, M. B. & Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395–398 (2013).
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).
Mei, A. et al. A hole-conductor–free, fully printable mesoscopic perovskite solar cell with high stability. Science 345, 295–298 (2014).
Yang, W. S. et al. High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science 348, 1234–1237 (2015).
Zhou, H. et al. Interface engineering of highly efficient perovskite solar cells. Science 345, 542–546 (2014).
Xiao, Z. et al. Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers. Energy Environ. Sci. 7, 2619–2623 (2014).
Liu, D. & Kelly, T. L. Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques. Nat. Photon. 8, 133–138 (2014).
Jeon, N. J. et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat. Mater. 13, 897–903 (2014).
Im, J.-H., Jang, I.-H., Pellet, N., Grätzel, M. & Park, N.-G. Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells. Nat. Nanotech. 9, 927–932 (2014).
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).
Tan, Z.-K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotech. 9, 687–692 (2014).
Cho, H. et al. Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes. Science 350, 1222–1225 (2015).
Li, G. et al. Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix. Nano Lett. 15, 2640–2644 (2015).
Sadhanala, A. et al. Blue-green color tunable solution processable organolead chloride–bromide mixed halide perovskites for optoelectronic applications. Nano Lett. 15, 6095–6101 (2015).
Gong, X. et al. Highly efficient quantum dot near-infrared light-emitting diodes. Nat. Photon. 10, 253–257 (2016).
Wang, Q. et al. Large fill-factor bilayer iodine perovskite solar cells fabricated by a low-temperature solution-process. Energy Environ. Sci. 7, 2359–2365 (2014).
Eperon, G. E., Burlakov, V. M., Docampo, P., Goriely, A. & Snaith, H. J. Morphological control for high performance, solution-processed planar heterojunction perovskite solar cells. Adv. Funct. Mater. 24, 151–157 (2014).
Xiao, M. et al. A fast deposition-crystallization procedure for highly efficient lead iodide perovskite thin-film solar cells. Angew. Chem. 126, 10056–10061 (2014).
Kerner, R. A., Zhao, L., Xiao, Z. & Rand, B. P. Ultrasmooth metal halide perovskite thin films via sol–gel processing. J. Mater. Chem. A 4, 8308–8315 (2016).
Mitzi, D., Wang, S., Feild, C., Chess, C. & Guloy, A. Conducting layered organic-inorganic halides containing <110>-oriented perovskite sheets. Science 267, 1473–1476 (1995).
Scholes, G. D. & Rumbles, G. Excitons in nanoscale systems. Nat. Mater. 5, 683–696 (2006).
Mitzi, D. B., Chondroudis, K. & Kagan, C. R. Organic-inorganic electronics. IBM J. Res. Dev. 45, 29–45 (2001).
Cheng, K.-Y., Anthony, R., Kortshagen, U. R. & Holmes, R. J. High-efficiency silicon nanocrystal light-emitting devices. Nano Lett. 11, 1952–1956 (2011).
Gauthron, K. et al. Optical spectroscopy of two-dimensional layered (C6H5C2H4-NH3)2-PbI4 perovskite. Opt. Express 18, 5912–5919 (2010).
Song, Z. et al. Impact of processing temperature and composition on the formation of methylammonium lead iodide perovskites. Chem. Mater. 27, 4612–4619 (2015).
Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotech. 11, 872–877 (2016).
Xiao, Z. et al. Giant switchable photovoltaic effect in organometal trihalide perovskite devices. Nat. Mater. 14, 193–198 (2015).
Shao, Y., Xiao, Z., Bi, C., Yuan, Y. & Huang, J. Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells. Nat. Commun. 5, 5784 (2014).
van Reenen, S., Kemerink, M. & Snaith, H. J. Modeling anomalous hysteresis in perovskite solar cells. J. Phys. Chem. Lett. 6, 3808–3814 (2015).
Schulz, P. et al. Interface energetics in organo-metal halide perovskite-based photovoltaic cells. Energy Environ. Sci. 7, 1377–1381 (2014).
Acknowledgements
We acknowledge a DARPA Young Faculty Award (award no. D15AP00093) for research funding. B.P.R. acknowledges the support of a DuPont Young Professor Award for research funding. R.A.K. acknowledges support from the National Science Foundation Graduate Research Fellowship under grant no. DGE 1148900.
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T.-W.K. and Z.X. designed the device structure. Z.X. performed the AFM, PL and absorption measurements, and fabricated the LEDs. R.A.K. developed the surfacted perovskite processing protocol, synthesized the precursors and helped to calculate grain size. L.Z. conducted the XRD and SEM measurements. N.L.T. and G.D.S conducted the TRPL and QY measurements. K.M.L. assisted with LED characterization. B.P.R. supervised the work. Z.X. and B.P.R. wrote the manuscript. All authors read and commented on the manuscript.
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Xiao, Z., Kerner, R., Zhao, L. et al. Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites. Nature Photon 11, 108–115 (2017). https://doi.org/10.1038/nphoton.2016.269
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DOI: https://doi.org/10.1038/nphoton.2016.269
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