Unveiling Zn Incorporation in CuInS(2) Quantum Dots: X‑ray and Optical Analysis of Doping Effects, Structural Modifications, and Surface Passivation

揭示锌掺杂到 CuInS(2) 量子点中的作用:掺杂效应、结构变化和表面钝化的 X 射线和光学分析

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Abstract

CuInS(2) quantum dots (QDs) have gained significant attention owing to their remarkable broadband emission, making them desirable for various optoelectronic applications requiring efficient luminescent nanomaterials. However, maximizing radiative recombination in CuInS(2) QDs necessitates minimizing intragap trap states. A common approach involves the introduction of Zn during the synthesis, which typically promotes the formation of a ZnS shell that passivates the QD surface. Despite its importance, the characterization and quantification of Zn incorporation using conventional techniques, such as optical spectroscopy or electron microscopy, remains challenging. In this study, we utilized X-ray absorption spectroscopy, in both X-ray absorption near-edge structure and extended X-ray absorption fine structure spectral ranges, to investigate Zn incorporation into CuInS(2) QDs, probing at the Zn, S, and Cu K-edges. This approach allowed us to detect the formation of a ZnS surface shell, tentatively quantifying its thickness, and to distinguish between Zn as a substituent at the shell or as an interstitial defect. Additionally, we explored the dynamical properties of CuInS(2) QDs using time-resolved optical spectroscopies, particularly in the presence of electron and hole acceptors (benzoquinone and phenothiazine), observing that hole transfer is highly sensitive to shell thickness. These results provide deeper insights into the Zn-induced shell.

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