Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology.

Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn(4+) as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors.

[1]  Tyler B Fleetham,et al.  Highly Efficient and Stable Narrow‐Band Phosphorescent Emitters for OLED Applications , 2015 .

[2]  Chang-Lyoul Lee,et al.  Multicolored Organic/Inorganic Hybrid Perovskite Light‐Emitting Diodes , 2015, Advanced materials.

[3]  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.

[4]  Cherie R. Kagan,et al.  Prospects of nanoscience with nanocrystals. , 2015, ACS nano.

[5]  Haizheng Zhong,et al.  Aggregation‐Induced Emission Features of Organometal Halide Perovskites and Their Fluorescence Probe Applications , 2015 .

[6]  A. Petrozza,et al.  Tuning the light emission properties by band gap engineering in hybrid lead halide perovskite. , 2014, Journal of the American Chemical Society.

[7]  H. Zeng,et al.  Strong covalency-induced recombination centers in perovskite solar cell material CH3NH3PbI3. , 2014, Journal of the American Chemical Society.

[8]  A. Bera,et al.  Temperature-dependent excitonic photoluminescence of hybrid organometal halide perovskite films. , 2014, Physical chemistry chemical physics : PCCP.

[9]  Mohammad Khaja Nazeeruddin,et al.  Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts , 2014, Science.

[10]  Adam Jaffe,et al.  Intrinsic white-light emission from layered hybrid perovskites. , 2014, Journal of the American Chemical Society.

[11]  Nakita K. Noel,et al.  Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic-inorganic lead halide perovskites. , 2014, ACS nano.

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

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

[14]  Angela S. Wochnik,et al.  Narrow-band red-emitting Sr[LiAl₃N₄]:Eu²⁺ as a next-generation LED-phosphor material. , 2014, Nature materials.

[15]  Sang Il Seok,et al.  Solvent engineering for high-performance inorganic-organic hybrid perovskite solar cells. , 2014, Nature materials.

[16]  Felix Deschler,et al.  Bright light-emitting diodes based on organometal halide perovskite. , 2014, Nature nanotechnology.

[17]  Prashant V. Kamat,et al.  Band filling with free charge carriers in organometal halide perovskites , 2014, Nature Photonics.

[18]  Yang Yang,et al.  Interface engineering of highly efficient perovskite solar cells , 2014, Science.

[19]  C. Murray,et al.  High-temperature photoluminescence of CdSe/CdS core/shell nanoheterostructures. , 2014, ACS nano.

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

[21]  Guglielmo Lanzani,et al.  Excitons versus free charges in organo-lead tri-halide perovskites , 2014, Nature Communications.

[22]  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.

[23]  Prashant V. Kamat,et al.  Recent advances in quantum dot surface chemistry. , 2014, ACS applied materials & interfaces.

[24]  Yanfa Yan,et al.  Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber , 2014 .

[25]  H. Snaith,et al.  The Raman Spectrum of the CH3NH3PbI3 Hybrid Perovskite: Interplay of Theory and Experiment. , 2014, The journal of physical chemistry letters.

[26]  G. Mínguez Espallargas,et al.  Nontemplate synthesis of CH3NH3PbBr3 perovskite nanoparticles. , 2014, Journal of the American Chemical Society.

[27]  J. Luther,et al.  Origin of the temperature dependence of the band gap of PbS and PbSe quantum dots , 2013 .

[28]  T. Mirkovic,et al.  Toward the Control of Nonradiative Processes in Semiconductor Nanocrystals. , 2013, The journal of physical chemistry letters.

[29]  Jieshan Qiu,et al.  High performance hybrid solar cells sensitized by organolead halide perovskites , 2013 .

[30]  V. Bulović,et al.  Emergence of colloidal quantum-dot light-emitting technologies , 2012, Nature Photonics.

[31]  J. Teuscher,et al.  Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites , 2012, Science.

[32]  Chongyin Yang,et al.  Low-temperature aluminum reduction of graphene oxide, electrical properties, surface wettability, and energy storage applications. , 2012, ACS nano.

[33]  M. Ikegami,et al.  Highly Luminescent Lead Bromide Perovskite Nanoparticles Synthesized with Porous Alumina Media , 2012 .

[34]  Byungki Kim,et al.  White‐Light‐Emitting Diodes with Quantum Dot Color Converters for Display Backlights , 2010, Advanced materials.

[35]  Alexey Y. Koposov,et al.  Effect of air exposure on surface properties, electronic structure, and carrier relaxation in PbSe nanocrystals. , 2010, ACS nano.

[36]  T. Miyasaka,et al.  Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. , 2009, Journal of the American Chemical Society.

[37]  Aidong Peng,et al.  Low‐Dimensional Nanomaterials Based on Small Organic Molecules: Preparation and Optoelectronic Properties , 2008 .

[38]  Yongfang Li,et al.  Bright, multicoloured light-emitting diodes based on quantum dots , 2007 .

[39]  N. Pradhan,et al.  Surface ligand dynamics in growth of nanocrystals. , 2007, Journal of the American Chemical Society.

[40]  P. Mulvaney,et al.  From Cd-rich to se-rich--the manipulation of CdSe nanocrystal surface stoichiometry. , 2007, Journal of the American Chemical Society.

[41]  Garry Rumbles,et al.  Excitons in nanoscale systems , 2006, Nature materials.

[42]  Yadong Yin,et al.  Colloidal nanocrystal synthesis and the organic–inorganic interface , 2005, Nature.

[43]  Takashi Kondo,et al.  Comparative study on the excitons in lead-halide-based perovskite-type crystals CH3NH3PbBr3 CH3NH3PbI3 , 2003 .

[44]  Jiayu Zhang,et al.  Surface-Related Emission in Highly Luminescent CdSe Quantum Dots , 2003 .

[45]  David B. Mitzi,et al.  Electroluminescence from an Organic−Inorganic Perovskite Incorporating a Quaterthiophene Dye within Lead Halide Perovskite Layers , 1999 .

[46]  Louis E. Brus,et al.  Luminescence Photophysics in Semiconductor Nanocrystals , 1999 .

[47]  Haller,et al.  Defects in semiconductors: some fatal, some vital , 1998, Science.

[48]  Tetsuo Tsutsui,et al.  Organic‐inorganic heterostructure electroluminescent device using a layered perovskite semiconductor (C6H5C2H4NH3)2PbI4 , 1994 .

[49]  Nobutsugu Minami,et al.  A Novel Preparation Method of Organic Microcrystals , 1992 .