Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as versatile photonic sources. Their processing and optoelectronic applications are hampered by the loss of colloidal stability and structural integrity due to the facile desorption of surface capping molecules during isolation and purification. To address this issue, herein, we propose a new ligand capping strategy utilizing common and inexpensive long-chain zwitterionic molecules such as 3-(N,N-dimethyloctadecylammonio)propanesulfonate, resulting in much improved chemical durability. In particular, this class of ligands allows for the isolation of clean NCs with high photoluminescence quantum yields (PL QYs) of above 90% after four rounds of precipitation/redispersion along with much higher overall reaction yields of uniform and colloidal dispersible NCs. Densely packed films of these NCs exhibit high PL QY values and effective charge transport. Consequently, they exhibit photoconductivity and low thresholds for amplified spontaneous emission of 2 μJ cm–2 under femtosecond optical excitation and are suited for efficient light-emitting diodes.

Cesium lead halide nanocrystals (CsPbX3 NCs) are new inorganic light sources covering the entire visible spectral range and exhibiting near-unity efficiencies. While the last years have seen rapid progress in green and red electroluminescence from CsPbX3 NCs, the development of blue counterparts remained rather stagnant. Controlling the surface state of CsPbX3 NCs had proven to be a major factor governing the efficiency of the charge injection and for diminishing the density of traps. Although didodecyldimethylammonium halides (DDAX; X = Br, Cl) had been known to improve the luminescence of CsPbX3 NCs when applied postsynthetically, they had not been used as the sole long-chain ammonium ligand directly in the synthesis of these NCs. Herein we report a facile, direct synthesis of DDAX-stabilized CsPbX3 NCs. We then demonstrate blue and green light-emitting diodes, characterized by the electroluminescence at 463–515 nm and external quantum efficiencies of 9.80% for green, 4.96% for sky-blue, and 1.03% for deep-blue spectral regions.

Hybrid organic–inorganic and fully inorganic lead halide perovskite nanocrystals (NCs) have recently emerged as versatile solution-processable light-emitting and light-harvesting optoelectronic materials. A particularly difficult challenge lies in warranting the practical utility of such semiconductor NCs in the red and infrared spectral regions. In this context, all three archetypal A-site monocationic perovskites—CH3NH3PbI3, CH(NH2)2PbI3, and CsPbI3—suffer from either chemical or thermodynamic instabilities in their bulk form. A promising approach toward the mitigation of these challenges lies in the formation of multinary compositions (mixed cation and mixed anion). In the case of multinary colloidal NCs, such as quinary CsxFA1–xPb(Br1–yIy)3 NCs, the outcome of the synthesis is defined by a complex interplay between the bulk thermodynamics of the solid solutions, crystal surface energies, energetics, dynamics of capping ligands, and the multiple effects of the reagents in solution. Accordingly, the rational synthesis of such NCs is a formidable challenge. Herein, we show that droplet-based microfluidics can successfully tackle this problem and synthesize CsxFA1–xPbI3 and CsxFA1–xPb(Br1–yIy)3 NCs in both a time- and cost-efficient manner. Rapid in situ photoluminescence and absorption measurements allow for thorough parametric screening, thereby permitting precise optical engineering of these NCs. In this showcase study, we fine-tune the photoluminescence maxima of such multinary NCs between 700 and 800 nm, minimize their emission line widths (to below 40 nm), and maximize their photoluminescence quantum efficiencies (up to 89%) and phase/chemical stabilities. Detailed structural analysis revealed that the CsxFA1–xPb(Br1–yIy)3 NCs adopt a cubic perovskite structure of FAPbI3, with iodide anions partially substituted by bromide ions. Most importantly, we demonstrate the excellent transference of reaction parameters from microfluidics to a conventional flask-based environment, thereby enabling up-scaling and further implementation in optoelectronic devices. As an example, CsxFA1–xPb(Br1–yIy)3 NCs with an emission maximum at 735 nm were integrated into light-emitting diodes, exhibiting a high external quantum efficiency of 5.9% and a very narrow electroluminescence spectral bandwidth of 27 nm.