Highly Luminescent and Stable Perovskite Nanocrystals with Octylphosphonic Acid as a Ligand for Efficient Light-Emitting Diodes.

All inorganic perovskite nanocrystals (NCs) of CsPbX3 (X = Cl, Br, I, or their mixture) are regarded as promising candidates for high-performance light-emitting diode (LED) owing to their high photoluminescence (PL) quantum yield (QY) and easy synthetic process. However, CsPbX3 NCs synthesized by the existing methods, where oleic acid (OA) and oleylamine (OLA) are generally used as surface-chelating ligands, suffer from poor stability due to the ligand loss, which drastically deteriorates their PL QY, as well as dispersibility in solvents. Herein, the OA/OLA ligands are replaced with octylphosphonic acid (OPA), which dramatically enhances the CsPbX3 stability. Owing to a strong interaction between OPA and lead atoms, the OPA-capped CsPbX3 (OPA-CsPbX3) NCs not only preserve their high PL QY (>90%) but also achieve a high-quality dispersion in solvents after multiple purification processes. Moreover, the organic residue in purified OPA-CsPbBr3 is only ∼4.6%, which is much lower than ∼29.7% in OA/OLA-CsPbBr3. Thereby, a uniform and compact OPA-CsPbBr3 film is obtained for LED application. A green LED with a current efficiency of 18.13 cd A-1, corresponding to an external quantum efficiency of 6.5%, is obtained. Our research provides a path to prepare high-quality perovskite NCs for high-performance optoelectronic devices.

[1]  Eric T. Hoke,et al.  A layered hybrid perovskite solar-cell absorber with enhanced moisture stability. , 2014, Angewandte Chemie.

[2]  Biwu Ma,et al.  Bright Light‐Emitting Diodes Based on Organometal Halide Perovskite Nanoplatelets , 2016, Advanced materials.

[3]  Nana Wang,et al.  Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells , 2016, Nature Photonics.

[4]  C. Shan,et al.  High-Efficiency and Air-Stable Perovskite Quantum Dots Light-Emitting Diodes with an All-Inorganic Heterostructure. , 2017, Nano letters.

[5]  Mohammad Khaja Nazeeruddin,et al.  One-Year stable perovskite solar cells by 2D/3D interface engineering , 2017, Nature Communications.

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

[7]  Noah D Bronstein,et al.  Essentially Trap-Free CsPbBr3 Colloidal Nanocrystals by Postsynthetic Thiocyanate Surface Treatment. , 2017, Journal of the American Chemical Society.

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

[9]  Yizheng Jin,et al.  Solution-processed, high-performance light-emitting diodes based on quantum dots , 2014, Nature.

[10]  D. Birnie Rational solvent selection strategies to combat striation formation during spin coating of thin films , 2001 .

[11]  Xiaogang Peng,et al.  Alternative Routes toward High Quality CdSe Nanocrystals , 2001 .

[12]  Weon-kyu Koh,et al.  Phosphonic Acid Stabilized Colloidal CsPbX3 (X=Br, I) Perovskite Nanocrystals and Their Surface Chemistry , 2016 .

[13]  Haihua Wu,et al.  A General Solvent Selection Strategy for Solution Processed Quantum Dots Targeting High Performance Light‐Emitting Diode , 2017 .

[14]  Richard H. Friend,et al.  Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes , 2015, Science.

[15]  J. Jasieniak,et al.  Stabilizing the cubic perovskite phase of CsPbI3 nanocrystals by using an alkyl phosphinic acid. , 2017, Chemical communications.

[16]  R. Friend,et al.  Amine-Based Passivating Materials for Enhanced Optical Properties and Performance of Organic-Inorganic Perovskites in Light-Emitting Diodes. , 2017, The journal of physical chemistry letters.

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

[18]  Lazaro A. Padilha,et al.  Controlling the influence of Auger recombination on the performance of quantum-dot light-emitting diodes , 2013, Nature Communications.

[19]  Haibo Zeng,et al.  Quantum Dot Light‐Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX3). , 2016 .

[20]  Q. Akkerman,et al.  Reversible Concentration-Dependent Photoluminescence Quenching and Change of Emission Color in CsPbBr3 Nanowires and Nanoplatelets. , 2017, The journal of physical chemistry letters.

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

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

[23]  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.

[24]  Dawei Di,et al.  Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix. , 2015, Nano letters.

[25]  Oleksandr Voznyy,et al.  Perovskite energy funnels for efficient light-emitting diodes. , 2016, Nature nanotechnology.

[26]  Xiao Wei Sun,et al.  All‐Inorganic Perovskite Nanocrystals for High‐Efficiency Light Emitting Diodes: Dual‐Phase CsPbBr3‐CsPb2Br5 Composites , 2016 .

[27]  L. Manna,et al.  Bright-Emitting Perovskite Films by Large-Scale Synthesis and Photoinduced Solid-State Transformation of CsPbBr3 Nanoplatelets. , 2017, ACS nano.

[28]  Henry J. Snaith,et al.  Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites , 2015, 1504.07025.

[29]  Zhenyu Yang,et al.  Amine‐Free Synthesis of Cesium Lead Halide Perovskite Quantum Dots for Efficient Light‐Emitting Diodes , 2016 .

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

[31]  Yuya Takeda,et al.  High-Efficiency Perovskite Quantum-Dot Light-Emitting Devices by Effective Washing Process and Interfacial Energy Level Alignment. , 2017, ACS applied materials & interfaces.

[32]  Heng Zhang,et al.  Inverted Quantum-Dot Light-Emitting Diodes Fabricated by All-Solution Processing. , 2016, ACS applied materials & interfaces.

[33]  Zhuang Liu,et al.  Efficient planar heterojunction perovskite solar cells employing graphene oxide as hole conductor. , 2014, Nanoscale.

[34]  Qingsong Shan,et al.  50‐Fold EQE Improvement up to 6.27% of Solution‐Processed All‐Inorganic Perovskite CsPbBr3 QLEDs via Surface Ligand Density Control , 2017, Advanced materials.

[35]  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.