Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals.

In the past few years, hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals have become one of the most interesting materials for optoelectronic applications. Here, we report a facile and rapid room temperature synthesis of 15-25 nm formamidinium CH(NH2)2PbX3 (X = Cl, Br, I, or mixed Cl/Br and Br/I) colloidal nanocrystals by ligand-assisted reprecipitation (LARP). The cubic and platelet-like nanocrystals with their emission in the range of 415-740 nm, full width at half-maximum (fwhm) of 20-44 nm, and radiative lifetimes of 5-166 ns enable band gap tuning by halide composition as well as by their thickness tailoring; they have a high photoluminescence quantum yield (up to 85%), colloidal and thermodynamic stability. Combined with surface modification that prevents degradation by water, this nanocrystalline material is an ideal candidate for optoelectronic devices and applications. In addition, optoelectronic measurements verify that the photodetector based on FAPbI3 nanocrystals paves the way for perovskite quantum dot photovoltaics.

[1]  Marco Brandl,et al.  Ligand-assisted thickness tailoring of highly luminescent colloidal CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets. , 2016, Chemical communications.

[2]  Lannoo,et al.  Calculation of the band gap for small CdS and ZnS crystallites. , 1989, Physical review. B, Condensed matter.

[3]  Iris Visoly-Fisher,et al.  Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials. , 2016, ChemSusChem.

[4]  Olga Malinkiewicz,et al.  Nontemplate synthesis of CH3NH3PbBr3 perovskite nanoparticles. , 2014, Journal of the American Chemical Society.

[5]  T. Miyasaka,et al.  Stability of solution-processed MAPbI3 and FAPbI3 layers. , 2016, Physical chemistry chemical physics : PCCP.

[6]  Richard H. Friend,et al.  Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals. , 2016, Journal of the American Chemical Society.

[7]  Jay B. Patel,et al.  Bandgap‐Tunable Cesium Lead Halide Perovskites with High Thermal Stability for Efficient Solar Cells , 2016 .

[8]  Weida Hu,et al.  Generalized colloidal synthesis of high-quality, two-dimensional cesium lead halide perovskite nanosheets and their applications in photodetectors. , 2016, Nanoscale.

[9]  H. Snaith,et al.  Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors , 2015, 1511.06507.

[10]  Haizheng Zhong,et al.  Water resistant CsPbX3 nanocrystals coated with polyhedral oligomeric silsesquioxane and their use as solid state luminophores in all-perovskite white light-emitting devices , 2016, Chemical science.

[11]  Yin Song,et al.  Structure‐Tuned Lead Halide Perovskite Nanocrystals , 2016, Advanced materials.

[12]  Edward H. Sargent,et al.  Planar-integrated single-crystalline perovskite photodetectors , 2015, Nature Communications.

[13]  J. Teuscher,et al.  Transforming Hybrid Organic Inorganic Perovskites by Rapid Halide Exchange , 2015 .

[14]  Eric T. Hoke,et al.  Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics† †Electronic supplementary information (ESI) available: Experimental details, PL, PDS spectra and XRD patterns. See DOI: 10.1039/c4sc03141e Click here for additional data file. , 2014, Chemical science.

[15]  Mircea Cotlet,et al.  Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution. , 2016, ACS nano.

[16]  P. Jain,et al.  Size Dependence of a Temperature-Induced Solid-Solid Phase Transition in Copper(I) Sulfide , 2011 .

[17]  F. Teng,et al.  Size-controlled synthesis of highly luminescent organometal halide perovskite quantum dots , 2016 .

[18]  A. Alivisatos,et al.  Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions. , 2016, Journal of the American Chemical Society.

[19]  J. Noh,et al.  Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. , 2013, Nano letters.

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

[21]  A. Weiss,et al.  Phase Diagrams of Quasibinary Systems of the Type: ABX3 — A′BX3; ABX3 — AB′X3, and ABX3 — ABX′3; X = Halogen , 1992 .

[22]  A Paul Alivisatos,et al.  Insight into the Ligand-Mediated Synthesis of Colloidal CsPbBr3 Perovskite Nanocrystals: The Role of Organic Acid, Base, and Cesium Precursors. , 2016, ACS nano.

[23]  Meng-Che Tsai,et al.  Organometal halide perovskite solar cells: degradation and stability , 2016 .

[24]  J. Vela,et al.  Persistent Dopants and Phase Segregation in Organolead Mixed-Halide Perovskites , 2016, Chemistry of Materials.

[25]  Namchul Cho,et al.  Perovskite Photodetectors Operating in Both Narrowband and Broadband Regimes , 2016, Advanced materials.

[26]  X. Duan,et al.  Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals , 2016, Nature Communications.

[27]  T. Miyasaka,et al.  HC(NH2)2PbI3 as a thermally stable absorber for efficient ZnO-based perovskite solar cells , 2016 .

[28]  S. Stranks,et al.  Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition. , 2016, ACS nano.

[29]  A Paul Alivisatos,et al.  Highly Luminescent Colloidal Nanoplates of Perovskite Cesium Lead Halide and Their Oriented Assemblies. , 2015, Journal of the American Chemical Society.

[30]  Shin-Tson Wu,et al.  Ultrastable, Highly Luminescent Organic–Inorganic Perovskite–Polymer Composite Films , 2016, Advanced materials.

[31]  S. Pang,et al.  Exceptional Morphology-Preserving Evolution of Formamidinium Lead Triiodide Perovskite Thin Films via Organic-Cation Displacement. , 2016, Journal of the American Chemical Society.

[32]  Peng Gao,et al.  Efficient luminescent solar cells based on tailored mixed-cation perovskites , 2016, Science Advances.

[33]  H. Demir,et al.  High brightness formamidinium lead bromide perovskite nanocrystal light emitting devices , 2016, Scientific Reports.

[34]  Chol-Jun Yu,et al.  Electronic structure, optical property and improved stability of mixed halide perovskite CH$_3$NH$_3$Pb(I$_{1-x}$Br$_x$)$_3$ by virtual crystal approximation within DFT , 2016 .

[35]  N. Zhu,et al.  Enhancing the Stability of CH3NH3PbBr3 Quantum Dots by Embedding in Silica Spheres Derived from Tetramethyl Orthosilicate in "Waterless" Toluene. , 2016, Journal of the American Chemical Society.

[36]  He Huang,et al.  Control of Emission Color of High Quantum Yield CH3NH3PbBr3 Perovskite Quantum Dots by Precipitation Temperature , 2015, Advanced science.

[37]  M. Al-Marri,et al.  Photo-stability of CsPbBr3 perovskite quantum dots for optoelectronic application , 2016, Science China Materials.

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

[39]  Alain Goriely,et al.  Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States , 2014 .

[40]  Min-Sang Lee,et al.  All-inorganic cesium lead halide perovskite nanocrystals for photodetector applications. , 2016, Chemical communications.

[41]  M. Kovalenko,et al.  Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals. , 2016, Nanoscale.

[42]  Liberato Manna,et al.  Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions , 2015, Journal of the American Chemical Society.

[43]  Young Chan Kim,et al.  Compositional engineering of perovskite materials for high-performance solar cells , 2015, Nature.

[44]  Song Jin,et al.  Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability. , 2016, Nano letters.

[45]  Miaoqiang Lyu,et al.  Composition-dependent photoluminescence intensity and prolonged recombination lifetime of perovskite CH3NH3PbBr(3-x)Cl(x) films. , 2014, Chemical communications.

[46]  Yu Tian,et al.  Fully Printed Halide Perovskite Light-Emitting Diodes with Silver Nanowire Electrodes. , 2016, ACS nano.

[47]  Anders Hagfeldt,et al.  Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells , 2016 .

[48]  Yu Tong,et al.  Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets. , 2015, Nano letters.

[49]  G. Gigli,et al.  The Bright Side of Perovskites. , 2016, The journal of physical chemistry letters.

[50]  H. Zeng,et al.  CsPbX3 Quantum Dots for Lighting and Displays: Room‐Temperature Synthesis, Photoluminescence Superiorities, Underlying Origins and White Light‐Emitting Diodes , 2016 .

[51]  Haizheng Zhong,et al.  Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology. , 2015, ACS nano.

[52]  Ayan A. Zhumekenov,et al.  Formamidinium Lead Halide Perovskite Crystals with Unprecedented Long Carrier Dynamics and Diffusion Length , 2016 .

[53]  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.

[54]  R. Costa,et al.  Light-Emitting Electrochemical Cells Based on Hybrid Lead Halide Perovskite Nanoparticles , 2015 .

[55]  Pooja Tyagi,et al.  Colloidal Organohalide Perovskite Nanoplatelets Exhibiting Quantum Confinement. , 2015, The journal of physical chemistry letters.

[56]  M. Saidaminov,et al.  Retrograde solubility of formamidinium and methylammonium lead halide perovskites enabling rapid single crystal growth. , 2015, Chemical communications.

[57]  W. Xu,et al.  Dehalogenative Homocoupling of Terminal Alkynyl Bromides on Au(111): Incorporation of Acetylenic Scaffolding into Surface Nanostructures. , 2016, ACS nano.

[58]  Antonietta Guagliardi,et al.  Monodisperse Formamidinium Lead Bromide Nanocrystals with Bright and Stable Green Photoluminescence , 2016, Journal of the American Chemical Society.

[59]  Chol-Jun Yu,et al.  Influence of halide composition on the structural, electronic, and optical properties of mixed CH 3 NH 3 Pb ( I 1 − x Br x ) 3 perovskites calculated using the virtual crystal approximation method , 2016, 1604.08497.

[60]  Giovanni Bertoni,et al.  Solution Synthesis Approach to Colloidal Cesium Lead Halide Perovskite Nanoplatelets with Monolayer-Level Thickness Control , 2016, Journal of the American Chemical Society.

[61]  J. Even,et al.  Photoexcitation dynamics in solution-processed formamidinium lead iodide perovskite thin films for solar cell applications , 2015, Light: Science & Applications.

[62]  M. Johnston,et al.  Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells , 2014 .

[63]  T. Bein,et al.  Stabilization of the Trigonal High-Temperature Phase of Formamidinium Lead Iodide. , 2015, The journal of physical chemistry letters.

[64]  Christopher H. Hendon,et al.  Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut , 2015, Nano letters.

[65]  Ashley R. Marshall,et al.  Quantum dot–induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics , 2016, Science.

[66]  Kidong Park,et al.  Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning. , 2015, Nano letters.