Efficient intraband hot carrier relaxation in Sn and Pb perovskite semiconductors mediated by strong electron-phonon coupling

The dynamic increase in terahertz photoconductivity resulting from energetic intraband relaxation was used to track the formation of highly mobile charges in thin films of the tin iodide perovskite Cs1-xRbxSnI3 and compared to the lead based Cs0:05(FA0:83MA0:17)0:95Pb(I0:83Br0:17)3. Energy relaxation times were found to be around 500 fs, comparable to those in GaAs and longer than the ones of the lead-based perovskite (around 300 fs). At low excess energies the efficient intraband relaxation can be understood within the context of the Frohlich electron-phonon interaction. For higher excess energies the photoconductivity rise time lengthens in accordance with carrier injection higher in the bands, or into multiple bands. The findings contribute to the development of design rules for photovoltaic devices capable of extracting hot carriers from perovskite semiconductors.

[1]  Song Jin,et al.  Screening in crystalline liquids protects energetic carriers in hybrid perovskites , 2016, Science.

[2]  R. Walton,et al.  Enhanced stability and efficiency in hole-transport-layer-free CsSnI3 perovskite photovoltaics , 2016, Nature Energy.

[3]  Laura M Herz,et al.  High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites , 2013, Advanced materials.

[4]  Edward H. Sargent,et al.  Perovskite photonic sources , 2016, Nature Photonics.

[5]  Neha Arora,et al.  Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20% , 2017, Science.

[6]  Yuanyuan Zhou,et al.  Long Minority‐Carrier Diffusion Length and Low Surface‐Recombination Velocity in Inorganic Lead‐Free CsSnI3 Perovskite Crystal for Solar Cells , 2017 .

[7]  R. Friend,et al.  Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites , 2015, Nature Communications.

[8]  S. Pang,et al.  Heterojunction‐Depleted Lead‐Free Perovskite Solar Cells with Coarse‐Grained B‐γ‐CsSnI3 Thin Films , 2016 .

[9]  Priti Tiwana,et al.  Electron mobility and injection dynamics in mesoporous ZnO, SnO₂, and TiO₂ films used in dye-sensitized solar cells. , 2011, ACS nano.

[10]  Matthew C. Beard,et al.  Transient photoconductivity in GaAs as measured by time-resolved terahertz spectroscopy , 2000 .

[11]  Jinsong Huang,et al.  Understanding the physical properties of hybrid perovskites for photovoltaic applications , 2017 .

[12]  David G. Cooke,et al.  Intrinsic femtosecond charge generation dynamics in single crystal CH3NH3PbI3 , 2015, 1507.02179.

[13]  Capasso,et al.  Direct subpicosecond measurement of carrier mobility of photoexcited electrons in gallium arsenide. , 1987, Physical review letters.

[14]  J. Luther,et al.  Observation of a hot-phonon bottleneck in lead-iodide perovskites , 2015, Nature Photonics.

[15]  J. Lloyd‐Hughes Generalized conductivity model for polar semiconductors at terahertz frequencies , 2012 .

[16]  Wei Zhang,et al.  Metal halide perovskites for energy applications , 2016, Nature Energy.

[17]  J. Lloyd‐Hughes,et al.  Efficient Intraband Hot Carrier Relaxation in the Perovskite Semiconductor Cs1–xRbxSnI3 Mediated by Strong Electron–Phonon Coupling , 2018, The Journal of Physical Chemistry C.

[18]  J. J. Wang,et al.  Synthesis and characterization of CsSnI3 thin films , 2010 .

[19]  Libai Huang,et al.  Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy , 2017, Science.

[20]  Laura M. Herz,et al.  Temperature‐Dependent Charge‐Carrier Dynamics in CH3NH3PbI3 Perovskite Thin Films , 2015 .

[21]  M. Johnston,et al.  The Effects of Doping Density and Temperature on the Optoelectronic Properties of Formamidinium Tin Triiodide Thin Films , 2018, Advanced materials.

[22]  Anders Hagfeldt,et al.  Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5ee03874j Click here for additional data file. , 2016, Energy & environmental science.

[23]  M. Johnston,et al.  Radiative Monomolecular Recombination Boosts Amplified Spontaneous Emission in HC(NH2)2SnI3 Perovskite Films. , 2016, The journal of physical chemistry letters.

[24]  Xiaoyang Zhu,et al.  Large polarons in lead halide perovskites , 2017, Science Advances.

[25]  Sandeep Kumar Pathak,et al.  High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors. , 2014, The journal of physical chemistry letters.

[26]  R. Friend,et al.  What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends. , 2016, Journal of the American Chemical Society.

[27]  M. Johnston,et al.  Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies. , 2016, Accounts of chemical research.

[28]  L. Herz Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits , 2017 .

[29]  Ralph,et al.  Subpicosecond photoconductivity of In0.53Ga0.47As: Intervalley scattering rates observed via THz spectroscopy. , 1996, Physical review. B, Condensed matter.

[30]  J. Lloyd‐Hughes,et al.  Cs1−xRbxSnI3 light harvesting semiconductors for perovskite photovoltaics , 2018 .

[31]  M. Bonn,et al.  Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films , 2017 .

[32]  Shah,et al.  Intervalley scattering in GaAs. , 1989, Physical review. B, Condensed matter.