Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites

Michael B. Price; Justinas Butkus; Tom C. Jellicoe; Aditya Sadhanala; Anouk Briane; Jonathan E. Halpert; Katharina Broch; Justin M. Hodgkiss; Richard H. Friend; Felix Deschler

doi:10.1038/ncomms9420

journal article Open Access Sep 25, 2015

Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites

Michael B. Price Justinas Butkus Tom C. Jellicoe Aditya Sadhanala

Anouk Briane Jonathan E. Halpert

Katharina Broch Justin M. Hodgkiss

Richard H. Friend

Felix Deschler

Nature Communications Vol. 6 No. 1 · Springer Science and Business Media LLC

View at Publisher Save 10.1038/ncomms9420

Abstract

AbstractMetal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a ‘phonon bottleneck’ substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon–impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.

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References

42

[1]

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites

Michael M. Lee, Joël Teuscher, Tsutomu Miyasaka et al.

Science 2012 10.1126/science.1228604

[2]

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) . 10.1038/srep00591

[3]

Jeon, N. J. et al. Compositional engineering of perovskite materials for high-performance solar cells. Nature 517, 476–480 (2015) . 10.1038/nature14133

[4]

Zhou, H. et al. Interface engineering of highly efficient perovskite solar cells. Science 345, 542–546 (2014) . 10.1126/science.1254050

[5]

Tan, Z.-K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotechnol. 9, 687–692 (2014) . 10.1038/nnano.2014.149

[6]

Deschler, F. et al. High photoluminescence efficiency and optically-pumped lasing in solution-processed mixed halide perovskite semiconductors. J. Phys. Chem. Lett. 5, 1421 (2014) . 10.1021/jz5005285

[7]

Xing, G. et al. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nat. Mater. 13, 476–480 (2014) . 10.1038/nmat3911

[8]

Zhang, Q., Ha, S. T., Liu, X., Sum, T. C. & Xiong, Q. Room-temperature near-infrared high-Q perovskite whispering-gallery planar nanolasers. Nano Lett. 14, 5995–6001 (2014) . 10.1021/nl503057g

[9]

Lin, Q. et al. Electro-optics of perovskite solar cells. Nat. Photon. 9, 106–112 (2014) . 10.1038/nphoton.2014.284

[10]

Ross, R. T. Efficiency of hot-carrier solar energy converters. J. Appl. Phys. 53, 3813 (1982) . 10.1063/1.331124

[11]

Mücke, O. D. & Wegener, M. Hot carrier induced picosecond dynamics of a vertical cavity surface emitting laser: Influence of transverse effects. Appl. Phys. Lett. 73, 569 (1998) . 10.1063/1.121858

[12]

Elsässer, M. et al. Subpicosecond switch-off and switch-on of a semiconductor laser due to transient hot carrier effects Subpicosecond switch-off and switch-on of a semiconductor laser due to transient hot carrier effects. Appl. Phys. Lett. 853, 1–4 (2013) .

[13]

Pavan, P., Bez, R., Olivo, P. & Zanoni, E. Flash memory cells-an overview. Proc. IEEE 85, 1248–1271 (1997) . 10.1109/5.622505

[14]

Shah, J. & Leite, R. C. C. Radiative recombination from photoexcited hot carriers in GaAs. Phys. Rev. Lett. 22, 22–25 (1969) . 10.1103/physrevlett.22.1304

[15]

Shah, J. Hot electrons and phonons under high intensity photoexcitation of semiconductors. Solid State Electron. 21, 43–50 (1978) . 10.1016/0038-1101(78)90113-2

[16]

Nuss, M. C., Auston, D. & Capasso, F. Direct subpicosecond measurement of carrier mobility of photoexcited electrons. Phys. Rev. Lett. 58, 2355–2358 (1987) . 10.1103/physrevlett.58.2355

[17]

Chen, K., Barker, A. J., Morgan, F. L. C., Halpert, J. E. & Hodgkiss, J. M. Effect of carrier thermalization dynamics on light emission and amplification in organometal halide perovskites. J. Phys. Chem. Lett. 6, 153 (2015) . 10.1021/jz502528c

[18]

Xiao, Z. et al. Giant switchable photovoltaic effect in organometal trihalide perovskite devices. Nat. Mater. 14, 1–7 (2014) .

[19]

Manser, J. S. & Kamat, P. V. Band filling with free charge carriers in organometal halide perovskites. Nat. Photon. 8, 737–743 (2014) . 10.1038/nphoton.2014.171

[20]

Stranks, S. D. et al. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013) . 10.1126/science.1243982

[21]

Xing, G. et al. Long-range balanced electron- and hole-transport lengths in organic-inorganic CH3NH3PbI3. Science 342, 344–347 (2013) . 10.1126/science.1243167

[22]

Zhang, W. et al. Ultra-smooth organic-inorganic perovskite thin-film formation and crystallization for Efficient Planar Heterojunction Solar Cells. Nat. Commun. 6, 6142 (2014) . 10.1038/ncomms7142

[23]

Shank, C. V., Fork, R. L., Leheny, R. F. & Shah, J. Dynamics of photoexcited GaAs band-edge absorption with subpicosecond resolution. Phys. Rev. Lett. 42, 112–115 (1979) . 10.1103/physrevlett.42.112

[24]

Shah, J. Photoexcited hot carriers: From cw to 6 fs in 20 Years. Solid State Electron. 32, 1051–1056 (1989) . 10.1016/0038-1101(89)90189-5

[25]

Rosenwaks, Y. et al. Hot-carrier cooling in GaAs: quantum wells versus bulk. Phys. Rev. B 48, 6–9 (1993) . 10.1103/physrevb.48.14675

[26]

Brivio, F. et al. Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal and cubic phases of methylammonium lead iodide. Preprint at <http://arXiv:1504.07508> (2015) . 10.1103/physrevb.92.144308

[27]

Skolnick, M. S. & Bimberg, D. Angular-dependent magnetoluminescence study of the layer compound 2H-PbI2. Phys. Rev. B 18, 7080 (1978) . 10.1103/physrevb.18.7080

[28]

Shah, J. Ultrafast Spectroscopy of Semiconductors and Semiconductor Nanostructures Springer (1999) . 10.1007/978-3-662-03770-6

[29]

Stamplecoskie, K. G., Manser, J. S. & Kamat, P. V. Dual nature of the excited state in organic-inorganic lead halide perovskites. Energy Environ. Sci. 8, 208–215 (2014) . 10.1039/c4ee02988g

[30]

S. M., Trevor, J. B., Geoffrey & E., Brian Semiconductor Opto-Electronics Butterworths (1973) .

[31]

Stern, F. Dispersion of the Index of Refraction Near the Absorption Edge of Semiconductors. Phys. Rev. 133, 1653 (1957) . 10.1103/physrev.133.a1653

[32]

Hecht, E. Optics Addison Wesley (1987) .

[33]

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) . 10.1016/s0038-1098(03)00566-0

[34]

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) . 10.1038/nphys3357

[35]

Brivio, F., Butler, K. T., Walsh, A. & van Schilfgaarde, M. Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers. Phys. Rev. B 89, 155204 (2014) . 10.1103/physrevb.89.155204

[36]

Umari, P., Mosconi, E. & De Angelis, F. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications. Sci. Rep. 4, 4467 (2014) . 10.1038/srep04467

[37]

Yablonovitch, E. & Kane, E. Reduction of lasing threshold current density by the lowering of valence band effective mass. J. Light. Technol. 4, 504–506 (1986) . 10.1109/jlt.1986.1074751

[38]

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) . 10.1002/adma.201305172

[39]

Menéndez-Proupin, E., Palacios, P., Wahnón, P. & Conesa, J. C. Self-consistent relativistic band structure of the CH3NH3PbI3 perovskite. Phys. Rev. B 90, 045207 (2014) . 10.1103/physrevb.90.045207

[40]

Filippetti, A. & Mattoni, A Hybrid perovskites for photovoltaics: Insights from first principles. Phys. Rev. B 89, 125203 (2014) . 10.1103/physrevb.89.125203

[41]

Edri, E. et al. Why lead methylammonium tri-iodide perovskite-based solar cells require a mesoporous electron transporting scaffold (but not necessarily a hole conductor). Nano Lett. 14, 1000–1004 (2014) . 10.1021/nl404454h

[42]

Barker, A. J., Chen, K. & Hodgkiss, J. M. Distance distributions of photogenerated charge pairs in organic photovoltaic cells. J. Am. Chem. Soc. 136, 12018–12026 (2014) . 10.1021/ja505380j

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Published: Sep 25, 2015
Vol/Issue: 6(1)
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Cite This Article

Michael B. Price, Justinas Butkus, Tom C. Jellicoe, et al. (2015). Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites. Nature Communications, 6(1). https://doi.org/10.1038/ncomms9420

Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites

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