Highly Luminescent Water-Dispersible NIR-Emitting Wurtzite CuInS₂/ZnS Core/Shell Colloidal Quantum Dots

Copper indium sulfide (CIS) quantum dots (QDs) are attractive as labels for biomedical imaging, since they have large absorption coefficients across a broad spectral range, size- and composition-tunable photoluminescence from the visible to the near-infrared, and low toxicity. However, the application of NIR-emitting CIS QDs is still hindered by large size and shape dispersions and low photoluminescence quantum yields (PLQYs). In this work, we develop an efficient pathway to synthesize highly luminescent NIR-emitting wurtzite CIS/ZnS QDs, starting from template Cu_2‑<i>x</i>S nanocrystals (NCs), which are converted by topotactic partial Cu⁺ for In³⁺ exchange into CIS NCs. These NCs are subsequently used as cores for the overgrowth of ZnS shells (≤1 nm thick). The CIS/ZnS core/shell QDs exhibit PL tunability from the first to the second NIR window (750–1100 nm), with PLQYs ranging from 75% (at 820 nm) to 25% (at 1050 nm), and can be readily transferred to water upon exchange of the native ligands for mercaptoundecanoic acid. The resulting water-dispersible CIS/ZnS QDs possess good colloidal stability over at least 6 months and PLQYs ranging from 39% (at 820 nm) to 6% (at 1050 nm). These PLQYs are superior to those of commonly available water-soluble NIR-fluorophores (dyes and QDs), making the hydrophilic CIS/ZnS QDs developed in this work promising candidates for further application as NIR emitters in bioimaging. The hydrophobic CIS/ZnS QDs obtained immediately after the ZnS shelling are also attractive as fluorophores in luminescent solar concentrators

Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Synthesis protocols for anisotropic CuInX₂ (X = S, Se, Te)-based heteronanocrystals (HNCs) are scarce due to the difficulty in balancing the reactivities of multiple precursors and the high solid-state diffusion rates of the cations involved in the CuInX₂ lattice. In this work, we report a multistep seeded growth synthesis protocol that yields colloidal wurtzite CuInS₂/ZnS dot core/rod shell HNCs with photoluminescence in the NIR (∼800 nm). The wurtzite CuInS₂ NCs used as seeds are obtained by topotactic partial Cu⁺ for In³⁺ cation exchange in template Cu_2–<i>x</i>S NCs. The seed NCs are injected in a hot solution of zinc oleate and hexadecylamine in octadecene, 20 s after the injection of sulfur in octadecene. This results in heteroepitaxial growth of wurtzite ZnS primarily on the Sulfur-terminated polar facet of the CuInS₂ seed NCs, the other facets being overcoated only by a thin (∼1 monolayer) shell. The fast (∼21 nm/min) asymmetric axial growth of the nanorod proceeds by addition of [ZnS] monomer units, so that the polarity of the terminal (002) facet is preserved throughout the growth. The delayed injection of the CuInS₂ seed NCs is crucial to allow the concentration of [ZnS] monomers to build up, thereby maximizing the anisotropic heteroepitaxial growth rates while minimizing the rates of competing processes (etching, cation exchange, alloying). Nevertheless, a mild etching still occurred, likely prior to the onset of heteroepitaxial overgrowth, shrinking the core size from 5.5 to ∼4 nm. The insights provided by this work open up new possibilities in designing multifunctional Cu-chalcogenide based colloidal heteronanocrystals

Highly Luminescent (Zn,Cd)Te/CdSe Colloidal Heteronanowires with Tunable Electron–Hole Overlap

We report the synthesis of ultranarrow (Zn,Cd)­Te/CdSe colloidal heteronanowires, using ZnTe magic size clusters as seeds. The wire formation starts with a partial Zn for Cd cation exchange, followed by self-organization into segmented heteronanowires. Further growth occurs by inclusion of CdSe. The heteronanowires emit in the 530 to 760 nm range with high quantum yields. The electron–hole overlap decreases with increasing CdSe volume fraction, allowing the optical properties to be controlled by adjusting the heteronanowire composition

Highly Luminescent (Zn,Cd)Te/CdSe Colloidal Heteronanowires with Tunable Electron–Hole Overlap

We report the synthesis of ultranarrow (Zn,Cd)­Te/CdSe colloidal heteronanowires, using ZnTe magic size clusters as seeds. The wire formation starts with a partial Zn for Cd cation exchange, followed by self-organization into segmented heteronanowires. Further growth occurs by inclusion of CdSe. The heteronanowires emit in the 530 to 760 nm range with high quantum yields. The electron–hole overlap decreases with increasing CdSe volume fraction, allowing the optical properties to be controlled by adjusting the heteronanowire composition