Kokilavani S, Selopal Gurpreet Singh, Jin Lei, Kumar Pawan, Barba David, Rosei Federico
Centre for Energy, Materials and Telecommunications, Institut national de la recherche scientifique, 1650 Boul. Lionel-Boulet, Varennes, QC, J3X 1P7, Canada.
Department of Engineering, Faculty of Agriculture, Dalhousie University, Truro, NS, B2N 5E3, Canada.
Chemistry. 2024 Oct 17;30(58):e202402026. doi: 10.1002/chem.202402026. Epub 2024 Oct 2.
Doping in semiconductor quantum dots (QDs) using optically active dopants tailors their optical, electronic, and magnetic properties beyond what is achieved by controlling size, shape, and composition. Herein, we synergistically modulated the optical properties of eco-friendly ZnInSe/ZnSe core/shell QDs by incorporating Cu-doping and Mn-alloying into their core and shell to investigate their use in anti-counterfeiting and information encryption. The engineered "Cu:ZnInSe/Mn:ZnSe" core/shell QDs exhibit an intense bright orange photoluminescence (PL) emission centered at 606 nm, with better color purity than the undoped and individually doped core/shell QDs. The average PL lifetime is significantly extended to 201 ns, making it relevant for complex encryption and anti-counterfeiting. PL studies reveal that in Cu:ZnInSe/Mn:ZnSe, the photophysical emission arises from the Cu state via radiative transition from the Mn T state. Integration of Cu:ZnInSe/Mn:ZnSe core/shell QDs into poly(methyl methacrylate) (PMMA) serves as versatile smart concealed luminescent inks for both writing and printing patterns. The features of these printed patterns using Cu:ZnInSe/Mn:ZnSe core/shell QDs persisted after 10 weeks of water-soaking and retained 70 % of PL emission intensity at 170 °C, demonstrating excellent thermal stability. This work provides an efficient approach to enhance both the emission and the stability of eco-friendly QDs via dopant engineering for fluorescence anti-counterfeiting applications.
使用具有光学活性的掺杂剂对半导体量子点（QDs）进行掺杂，可以调整其光学、电子和磁学性质，这超出了通过控制尺寸、形状和组成所能达到的范围。在此，我们通过在其核壳结构中引入铜掺杂和锰合金化，协同调制了环保型ZnInSe/ZnSe核壳量子点的光学性质，以研究它们在防伪和信息加密中的应用。经过工程设计的“Cu:ZnInSe/Mn:ZnSe”核壳量子点在606nm处呈现出强烈的亮橙色光致发光（PL）发射，其颜色纯度优于未掺杂和单独掺杂的核壳量子点。平均PL寿命显著延长至201ns，这使其适用于复杂的加密和防伪应用。PL研究表明，在Cu:ZnInSe/Mn:ZnSe中，光物理发射源于Cu态通过Mn T态的辐射跃迁。将Cu:ZnInSe/Mn:ZnSe核壳量子点集成到聚甲基丙烯酸甲酯（PMMA）中，可作为用于书写和印刷图案的通用智能隐形发光油墨。使用Cu:ZnInSe/Mn:ZnSe核壳量子点的这些印刷图案的特征在水浸10周后仍然存在，并且在170°C下保留了70%的PL发射强度，证明了其优异的热稳定性。这项工作提供了一种有效的方法，通过掺杂剂工程来提高环保型量子点的发射和稳定性，用于荧光防伪应用。
