Ternary and quaternary colloidal nanocrystals (NCs) based on I–III–VI group semiconductors are promising low-toxic luminescent materials attracting huge interest as alternatives to cadmium- and lead-chalcogenide-based NCs. Despite significant progress in the synthesis of three-dimensionally confined quantum dots based on I–III–VI semiconductors with intensive photoluminescence (PL) in a broad spectral range, all attempts to prepare one-dimensionally confined nanoplatelets (NPLs) or nanosheets have resulted in rather nonemitting two-dimensional (2D) NCs. Since 2D NCs of the II–VI group exhibit unique anisotropic optical properties, exploring synthetic strategies to obtain 2D I–III–VI-based NPLs might also reveal interesting optical and electronic features. In this work, we demonstrate the synthesis of luminescent In-rich Cu–Zn–In–S (CZIS) NPLs using a one-pot approach. The synthesis includes the formation of Cu–In–S NPLs from In2S3 seeds, followed by the incorporation of zinc to form quaternary NPLs with improved stability and optical properties. The synthetic strategy implemented results in the formation of ∼1 nm thick NPLs with lateral sizes of ∼30 × 10 nm2 and a tetragonal crystal structure. As-synthesized NPLs are stable at ambient conditions and demonstrate PL in the range of 700–800 nm with a large Stokes shift. An additional shell of ZnS grown on CZIS NPLs resulted in the enhancement of their PL quantum yield reaching 29%.
Copper chalcogenide-based nanocrystals (NCs) are a suitable replacement for toxic Cd/Pb chalcogenide-based NCs in a wide range of applications including photovoltaics, optoelectronics, and biological imaging. However, despite rigorous research, direct synthesis approaches of this class of compounds suffer from inhomogeneous size, shape, and composition of the NC ensembles, which is reflected in their broad photoluminescence (PL) bandwidths. A partial cation exchange (CE) strategy, wherein host cations in the initial binary copper chalcogenide are replaced by incoming cations to form ternary/quaternary multicomponent NCs, has been proven to be instrumental in achieving better size, shape, and composition control to this class of nanomaterials. Additionally, adopting synthetic strategies which help to eliminate inhomogeneities in the NC ensembles can lead to narrower PL bandwidths, as was shown by single-particle studies on I−III−VI 2 -based semiconductor NCs. In this work, we formulate a two-step colloidal synthesis of Cu−Zn−In−Se (CZISe) NCs via a partial CE pathway. The first step is the synthesis of Cu 2−x Se NCs, which serve as a template for the subsequent CE reaction. The second step is the incorporation of the In 3+ and Zn 2+ guest cations into the synthesized Cu 2−x Se NCs via simultaneous injection of both metal precursors, which results in gradient-alloyed CZISe NCs with a Zn-rich surface. The as-synthesized NCs exhibit near-infrared (NIR) PL without an additional shell growth, which is typically required in most of the developed protocols. The photoluminescence quantum yield (PLQY) of these Cu chalcogenide-based NCs reaches 20%. These NCs also exhibit intriguingly narrow PL bands, which challenges the notion of broad PL bands being an inherent property of this class of NCs. Additionally, a variation in the feed ratios of the incoming cations, i.e., In/Zn, results in the variation of the composition of the synthesized NCs. Henceforth, the optical properties of these NCs could be tuned by a simple variation of the composition of the NCs achieved by varying the feed ratios of the incoming cations. Within a narrow size distribution, the PL maxima range from 980 to 1060 nm, depending on the composition of the NCs. Post-synthetic surface modification of the synthesized NCs enabled the replacement of the parent long-chain organic ligands with smaller species, which is essential for their prospective applications requiring efficient charge transport. With PL emission extended into the NIR, the synthesized NCs are suitable for an array of potential applications, most importantly in the area of solar energy harvesting and bioimaging. The large Stokes shift inherent to these materials, their absorption in the solar range, and their NIR PL within the biological window make them suitable candidates.
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