Encapsulation of Perovskite Nanocrystals into Macroscale Polymer Matrices: Enhanced Stability and Polarization.

Lead halide perovskites hold promise for photonic devices, due to their superior optoelectronic properties. However, their use is limited by poor stability and toxicity. We demonstrate enhanced water and light stability of high-surface-area colloidal perovskite nanocrystals by encapsulation of colloidal CsPbBr3 quantum dots into matched hydrophobic macroscale polymeric matrices. This is achieved by mixing the quantum dots with presynthesized high-molecular-weight polymers. We monitor the photoluminescence quantum yield of the perovskite-polymer nanocomposite films under water-soaking for the first time, finding no change even after >4 months of continuous immersion in water. Furthermore, photostability is greatly enhanced in the macroscale polymer-encapsulated nanocrystal perovskites, which sustain >1010 absorption events per quantum dot prior to photodegradation, a significant threshold for potential device use. Control of the quantum dot shape in these thin-film polymer composite enables color tunability via strong quantum-confinement in nanoplates and significant room temperature polarized emission from perovskite nanowires. Not only does the high-molecular-weight polymer protect the perovskites from the environment but also no escaped lead was detected in water that was in contact with the encapsulated perovskites for months. Our ligand-passivated perovskite-macroscale polymer composites provide a robust platform for diverse photonic applications.

[1]  Noah D Bronstein,et al.  Tracking Nanoparticle Diffusion and Interaction during Self-Assembly in a Liquid Cell. , 2017, Nano letters.

[2]  Weidong Yang,et al.  Linearly Polarized Emission from Colloidal Semiconductor Quantum Rods , 2001, Science.

[3]  Zeger Hens,et al.  Highly Dynamic Ligand Binding and Light Absorption Coefficient of Cesium Lead Bromide Perovskite Nanocrystals. , 2016, ACS nano.

[4]  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.

[5]  Daniele Gerion,et al.  Fluorescent CdSe/ZnS nanocrystal-peptide conjugates for long-term, nontoxic imaging and , 2004 .

[6]  D. Sadoway Block and graft copolymer electrolytes for high-performance, solid-state, lithium batteries , 2004 .

[7]  David J. Nesbitt,et al.  ``On''/``off'' fluorescence intermittency of single semiconductor quantum dots , 2001 .

[8]  Mikael Kubista,et al.  Experimental correction for the inner-filter effect in fluorescence spectra , 1994 .

[9]  Liberato Manna,et al.  X-ray Lithography on Perovskite Nanocrystals Films: From Patterning with Anion-Exchange Reactions to Enhanced Stability in Air and Water , 2015, ACS nano.

[10]  Speciality Polymers / Polymer Physics , 1989 .

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

[12]  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.

[13]  Liwei Lin,et al.  Strain-dependent dynamic mechanical properties of Kevlar to failure: Structural correlations and comparisons to other polymers , 2015 .

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

[15]  M. Nikl,et al.  Polarized luminescence of CsPbBr3 nanocrystals (quantum dots) in CsBr:Pb single crystal , 1999 .

[16]  M. Grätzel The light and shade of perovskite solar cells. , 2014, Nature materials.

[17]  Xiao Wei Sun,et al.  Polarized emission from CsPbX3 perovskite quantum dots. , 2016, Nanoscale.

[18]  Tomas Leijtens,et al.  Carbon nanotube/polymer composites as a highly stable hole collection layer in perovskite solar cells. , 2014, Nano letters.

[19]  Aziz Genç,et al.  Polymer-Enhanced Stability of Inorganic Perovskite Nanocrystals and Their Application in Color Conversion LEDs. , 2016, ACS applied materials & interfaces.

[20]  Noah D Bronstein,et al.  Quantum Dot Luminescent Concentrator Cavity Exhibiting 30-fold Concentration , 2015 .

[21]  Haibo Zeng,et al.  Photon Driven Transformation of Cesium Lead Halide Perovskites from Few‐Monolayer Nanoplatelets to Bulk Phase , 2016, Advanced materials.

[22]  C. Bai,et al.  Single molecule chemistry and physics , 2006 .

[23]  Henry J. Snaith,et al.  Stability of Metal Halide Perovskite Solar Cells , 2015 .

[24]  L. Ionov,et al.  New insight into icing and de-icing properties of hydrophobic and hydrophilic structured surfaces based on core-shell particles. , 2015, Soft matter.

[25]  Yang Yang,et al.  Solution-processed hybrid perovskite photodetectors with high detectivity , 2014, Nature Communications.

[26]  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.

[27]  Wilfried van Sark,et al.  Photooxidation and Photobleaching of Single CdSe/ZnS Quantum Dots Probed by Room-Temperature Time-Resolved Spectroscopy , 2001 .

[28]  Aram Amassian,et al.  Ligand-Stabilized Reduced-Dimensionality Perovskites. , 2016, Journal of the American Chemical Society.

[29]  Ru‐Shi Liu,et al.  Mesoporous Silica Particles Integrated with All-Inorganic CsPbBr3 Perovskite Quantum-Dot Nanocomposites (MP-PQDs) with High Stability and Wide Color Gamut Used for Backlight Display. , 2016, Angewandte Chemie.

[30]  Xiangfeng Duan,et al.  Highly Polarized Photoluminescence and Photodetection from Single Indium Phosphide Nanowires , 2001, Science.

[31]  Genner, Sarah ON-OFF , 2016 .

[32]  David Cahen,et al.  How Important Is the Organic Part of Lead Halide Perovskite Photovoltaic Cells? Efficient CsPbBr3 Cells. , 2015, The journal of physical chemistry letters.

[33]  K. Johnston,et al.  Contact angle of water on polystyrene thin films: effects of CO(2) environment and film thickness. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[34]  David Cahen,et al.  Rain on Methylammonium Lead Iodide Based Perovskites: Possible Environmental Effects of Perovskite Solar Cells. , 2015, The journal of physical chemistry letters.

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

[36]  P. Yang,et al.  Solution‐Phase Synthesis of Cesium Lead Halide Perovskite Nanowires. , 2015 .

[37]  I. Luzinov,et al.  Ultrahydrophobic textile surface via decorating fibers with monolayer of reactive nanoparticles and non-fluorinated polymer. , 2007, Chemical communications.

[38]  Sandeep Kumar Pathak,et al.  Perovskite Crystals for Tunable White Light Emission , 2015 .

[39]  M. Ko,et al.  Enhancing Stability of Perovskite Solar Cells to Moisture by the Facile Hydrophobic Passivation. , 2015, ACS applied materials & interfaces.

[40]  Xingyi Huang,et al.  Protection of SEBS/PS Blends against Gamma Radiation by Aromatic Compounds , 2009 .

[41]  Liwei Lin,et al.  Influence of three-dimensional nanoparticle branching on the Young’s modulus of nanocomposites: Effect of interface orientation , 2015, Proceedings of the National Academy of Sciences.

[42]  Liwei Lin,et al.  Cavitation-Induced Stiffness Reductions in Quantum Dot–Polymer Nanocomposites , 2016 .

[43]  Bernd Rech,et al.  A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells , 2016, Science.

[44]  Manas R. Parida,et al.  Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission. , 2015, The journal of physical chemistry letters.

[45]  Shaojun Guo,et al.  Room Temperature Single-Photon Emission from Individual Perovskite Quantum Dots. , 2015, ACS nano.

[46]  Padhraic Mulligan,et al.  Sensitive X-ray detectors made of methylammonium lead tribromide perovskite single crystals , 2016, Nature Photonics.

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

[48]  Vincent Noireaux,et al.  In Vivo Imaging of Quantum Dots Encapsulated in Phospholipid Micelles , 2002, Science.

[49]  E. Thomas,et al.  Block Copolymer Nanocomposites: Perspectives for Tailored Functional Materials , 2005, Advanced materials.

[50]  Liwei Lin,et al.  Tetrapod nanocrystals as fluorescent stress probes of electrospun nanocomposites. , 2013, Nano letters.

[51]  S. Basu,et al.  Continuous dynamic analysis: evolution of elastic properties with strain , 2014 .

[52]  Nam-Gyu Park,et al.  6.5% efficient perovskite quantum-dot-sensitized solar cell. , 2011, Nanoscale.

[53]  S. Govindjee,et al.  Mechanisms of Local Stress Sensing in Multifunctional Polymer Films Using Fluorescent Tetrapod Nanocrystals. , 2016, Nano letters.

[54]  Oleksandr Voznyy,et al.  Highly Efficient Perovskite‐Quantum‐Dot Light‐Emitting Diodes by Surface Engineering , 2016, Advanced materials.