Controlling the structure of colloidal nanocrystals (NCs) is key to the generation of their complex functionality. This requires an understanding of the NC surface at the atomic level. The structure of colloidal PbS NCs passivated with oleic acid has been studied theoretically and experimentally. We show the existence of surface OH(-) groups, which play a key role in stabilizing the PbS(111) facets, consistent with x-ray photoelectron spectroscopy as well as other spectroscopic and chemical experiments. The role of water in the synthesis process is also revealed. Our model, along with existing observations of NC surface termination and passivation by ligands, helps to explain and predict the properties of NCs and their assemblies.
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http://dx.doi.org/10.1126/science.1252727 | DOI Listing |
ACS Nano
July 2024
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Photoluminescence intermittency remains one of the biggest challenges in realizing perovskite quantum dots (QDs) as scalable single photon emitters. We compare CsPbBr QDs capped with different ligands, lecithin, and a combination of oleic acid and oleylamine, to elucidate the role of surface chemistry on photoluminescence intermittency. We employ widefield photoluminescence microscopy to sample the blinking behavior of hundreds of QDs.
View Article and Find Full Text PDFSmall Methods
December 2024
Faculty of Informatics and Engineering, The University of Electro Communications, Tokyo, 1828585, Japan.
Nowadays, the extensively used lead sulfide (PbS) quantum dot (QD) hole transport layer (HTL) relies on layer-by-layer method to replace long chain oleic acid (OA) ligands with short 1,2-ethanedithiol (EDT) ligands for preparation. However, the inevitable significant volume shrinkage caused by this traditional method will result in undesired cracks and disordered QD arrangement in the film, along with adverse increased defect density and inhomogeneous energy landscape. To solve the problem, a novel method for EDT passivated PbS QD (PbS-EDT) HTL preparation using small-sized benzoic acid (BA) as intermediate ligands is proposed in this work.
View Article and Find Full Text PDFNanoscale
April 2024
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
Inorganic cesium lead bromide nanocrystals (CsPbBr NCs) hold promising prospects for high performance green light-emitting diodes (LEDs) due to their exceptional color purity and high luminescence efficiency. However, the common ligands employed for passivating these indispensable NCs, such as long-chain organic ligands like oleic acid and oleylamine (OA/OAm), display highly dynamic binding and electronic insulating issues, thereby resulting in a low efficiency of the as-fabricated LEDs. Herein, we report a new zwitterionic short-branched alkyl sulfobetaine ligand, namely trioctyl(propyl-3-sulfonate) ammonium betaine (TOAB), to passivate CsPbBr NCs a feasible one-step solution synthesis, enabling efficiency improvement of CsPbBr NC-based LEDs.
View Article and Find Full Text PDFNanomaterials (Basel)
February 2024
Faculty of Informatics and Engineering, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585, Japan.
CsNaInCl double perovskites, which have excellent photoelectric conversion properties and are non-toxic and lead-free, have recently gained significant attention. In particular, double-perovskite quantum dots (QDs) are viewed as a promising material for optoelectronic device applications. Ligands such as oleic acid (OA) and oleylamine (OAm) are essential for the synthesis of perovskite QDs, but their specific roles in double-perovskite QDs remain unclear.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2024
Department of Chemical Physics, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
We report a mechanistic study of the photoluminescence (PL) enhancement in CsPbBr perovskite nanocrystals (PNCs) induced by organic/inorganic hybrid ligand engineering. Compared to the as-synthesized oleic acid-oleylamine modified PNCs, the tributylphosphine oxide-CaBr modified PNCs can achieve a better passivation effect due to strong P═O-Pb coordination and Br-vacancy remedy, resulting in enhanced PL efficiency. We employ steady-state/time-resolved/temperature-dependent PL and fluence/polarization-dependent ultrafast transient absorption spectroscopy to obtain a mechanistic understanding of such an enhancement effect from both nonradiative and radiative perspectives.
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