Radiative Monomolecular Recombination Boosts Amplified Spontaneous Emission in HC(NH2)2SnI3 Perovskite Films.

Hybrid metal-halide perovskites have potential as cost-effective gain media for laser technology because of their superior optoelectronic properties. Although lead-halide perovskites have been most widely studied to date, tin-based perovskites have been proposed as a less toxic alternative. In this Letter, we show that amplified spontaneous emission (ASE) in formamidinium tin triiodide (FASnI3) thin films is supported by an observed radiative monomolecular charge recombination pathway deriving from its unintentional doping. Such a radiative component will be active even at the lowest charge-carrier densities, opening a pathway for ultralow light-emission thresholds. Using time-resolved THz photoconductivity analysis, we further show that the material has an unprecedentedly high charge-carrier mobility of 22 cm2 V-1 s-1 favoring efficient transport. In addition, FASnI3 exhibits strong radiative bimolecular recombination and Auger rates that are over an order of magnitude lower than for lead-halide perovskites. In combination, these properties reveal that tin-halide perovskites are highly suited to light-emitting devices.

[1]  Sandeep Kumar Pathak,et al.  Lead-free organic–inorganic tin halide perovskites for photovoltaic applications , 2014 .

[2]  S. Mhaisalkar,et al.  Perovskite Materials for Light‐Emitting Diodes and Lasers , 2016 .

[3]  Hiroyuki Hasegawa,et al.  Hall mobility in tin iodide perovskite CH{sub 3}NH{sub 3}SnI{sub 3}: Evidence for a doped semiconductor , 2013 .

[4]  R. Paschotta Amplified Spontaneous Emission , 2010 .

[5]  Laura M Herz,et al.  Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH3NH3PbI3-xClx. , 2014, The journal of physical chemistry letters.

[6]  H. Bolink,et al.  Trap‐Assisted Non‐Radiative Recombination in Organic–Inorganic Perovskite Solar Cells , 2015, Advanced materials.

[7]  James Lloyd-Hughes,et al.  A Review of the Terahertz Conductivity of Bulk and Nano-Materials , 2012 .

[8]  Feliciano Giustino,et al.  Electron–phonon coupling in hybrid lead halide perovskites , 2016, Nature Communications.

[9]  Mercouri G Kanatzidis,et al.  Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. , 2013, Inorganic chemistry.

[10]  E. Hendry,et al.  Carrier dynamics in semiconductors studied with time-resolved terahertz spectroscopy , 2011 .

[11]  Qingfeng Dong,et al.  Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination , 2015, Nature Photonics.

[12]  X. Gong,et al.  Influence of Defects and Synthesis Conditions on the Photovoltaic Performance of Perovskite Semiconductor CsSnI3 , 2014 .

[13]  Jay B. Patel,et al.  Structured Organic–Inorganic Perovskite toward a Distributed Feedback Laser , 2016, Advanced materials.

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

[15]  V. Sundström,et al.  Intrinsic complications in the analysis of optical-pump, terahertz probe experiments , 2005 .

[16]  Jay B. Patel,et al.  Enhanced Amplified Spontaneous Emission in Perovskites Using a Flexible Cholesteric Liquid Crystal Reflector. , 2015, Nano letters.

[17]  G. Eperon,et al.  Charge Carriers in Planar and Meso-Structured Organic-Inorganic Perovskites: Mobilities, Lifetimes, and Concentrations of Trap States. , 2015, The journal of physical chemistry letters.

[18]  M. Johnston,et al.  Effect of Structural Phase Transition on Charge-Carrier Lifetimes and Defects in CH3NH3SnI3 Perovskite. , 2016, The journal of physical chemistry letters.

[19]  Henry J. Snaith,et al.  Efficient planar heterojunction perovskite solar cells by vapour deposition , 2013, Nature.

[20]  Giovanni Bongiovanni,et al.  Correlated electron–hole plasma in organometal perovskites , 2014, Nature Communications.

[21]  H. Lashuel,et al.  Health hazards of methylammonium lead iodide based perovskites: cytotoxicity studies. , 2016, Toxicology research.

[22]  M. Grätzel,et al.  Solution‐Processed Tin‐Based Perovskite for Near‐Infrared Lasing , 2016, Advanced materials.

[23]  Hyun Suk Jung,et al.  Perovskite solar cells: from materials to devices. , 2015, Small.

[24]  David S. Ginger,et al.  Photoluminescence Lifetimes Exceeding 8 μs and Quantum Yields Exceeding 30% in Hybrid Perovskite Thin Films by Ligand Passivation , 2016 .

[25]  V. Klimov Multicarrier Interactions in Semiconductor Nanocrystals in Relation to the Phenomena of Auger Recombination and Carrier Multiplication , 2014 .

[26]  W. Read,et al.  Statistics of the Recombinations of Holes and Electrons , 1952 .

[27]  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.

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

[29]  Nripan Mathews,et al.  Lead‐Free Halide Perovskite Solar Cells with High Photocurrents Realized Through Vacancy Modulation , 2014, Advanced materials.

[30]  Prashant V Kamat,et al.  Intriguing Optoelectronic Properties of Metal Halide Perovskites. , 2016, Chemical reviews.

[31]  Hao Li,et al.  CsSnI3: Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions. , 2012, Journal of the American Chemical Society.

[32]  Yongbo Yuan,et al.  Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells , 2014, Nature Communications.

[33]  Philippe Caroff,et al.  Doping-enhanced radiative efficiency enables lasing in unpassivated GaAs nanowires , 2016, Nature Communications.

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

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

[36]  M. Fiebig,et al.  Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites , 2015, Nature Communications.

[37]  Yukihiro Takahashi,et al.  Hall Mobility in Tin Iodide Perovskite CH3NH3SnI3: Evidence for a Doped Semiconductor. , 2013 .

[38]  A. Haug Temperature dependence of Auger recombination in gallium antimonide , 1984 .

[39]  Laura M. Herz,et al.  Charge-Carrier Dynamics in Organic-Inorganic Metal Halide Perovskites. , 2016, Annual review of physical chemistry.

[40]  G A Turnbull,et al.  Organic semiconductor lasers. , 2007, Chemical reviews.

[41]  Markus Pollnau,et al.  Organic solid‐state integrated amplifiers and lasers , 2012 .

[42]  Robert P. H. Chang,et al.  Lead-free solid-state organic–inorganic halide perovskite solar cells , 2014, Nature Photonics.

[43]  M. Sheik-Bahae,et al.  Can laser light cool semiconductors? , 2004, Physical review letters.

[44]  M. Amann,et al.  Dynamics of amplified spontaneous emission in InAs/GaAs quantum dots , 2000 .

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

[46]  Yelin Deng,et al.  Life Cycle Assessment of Titania Perovskite Solar Cell Technology for Sustainable Design and Manufacturing. , 2015, ChemSusChem.

[47]  Wei Lin Leong,et al.  Formamidinium tin-based perovskite with low Eg for photovoltaic applications , 2015 .

[48]  L. Allen,et al.  Amplified spontaneous emission I. The threshold condition , 1971 .

[49]  C. Ciesla,et al.  Suppression of non-radiative processes in semiconductor mid-infrared emitters and detectors , 1997 .

[50]  Song Jin,et al.  Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors. , 2015, Nature materials.

[51]  Nripan Mathews,et al.  Low-temperature solution-processed wavelength-tunable perovskites for lasing. , 2014, Nature materials.

[52]  J. Even,et al.  Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications , 2013 .

[53]  R. Walton,et al.  Tin perovskite/fullerene planar layer photovoltaics: improving the efficiency and stability of lead-free devices , 2015 .

[54]  Paolo Umari,et al.  Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications , 2014, Scientific Reports.

[55]  J. Even,et al.  DFT and k · p modelling of the phase transitions of lead and tin halide perovskites for photovoltaic cells , 2014 .