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

Unravelling the Size and Temperature Dependence of Exciton Lifetimes in Colloidal ZnSe Quantum Dots

We report on the temperature dependence of the band-edge photoluminescence decay of organically capped colloidal ZnSe quantum dots (QDs) in the size range from 4.0 to 7.5 nm. A similar trend is observed for all investigated sizes: the decay time is short (∼5 ns) above 20 K and increases sharply below 20 K, eventually reaching a constant value (270–400 ns) at sufficiently low temperatures (<4 K). The temperature regime in which the decrease of lifetime occurs depends on the QD size and is lower for larger QDs. This behavior can be modeled by a Boltzmann distribution between a lower long-lived and a higher short-lived exciton states, with an energy separation ranging from 3.3 ± 0.2 to 1.5 ± 0.1 meV in the 4.0 ± 0.3 to 7.5 ± 0.5 nm size range. We show that this energy separation is consistent with coupling of the lowest exciton state to a confined acoustic phonon

Formation of Colloidal Copper Indium Sulfide Nanosheets by Two-Dimensional Self-Organization

Colloidal 2D semiconductor nanosheets (NSs) are an interesting new class of materials due to their unique properties. However, synthesis of these NSs is challenging, and synthesis procedures for materials other than the well-known Pb- and Cd-chalcogenides are still underdeveloped. In this paper, we present a new approach to make copper indium sulfide (CIS) NSs and study their structural and optical properties. The CIS NSs form via self-organization and oriented attachment of 2.5 nm chalcopyrite CuInS₂ nanocrystals (NCs), yielding triangular- and hexagonal-shaped NSs with a thickness of ∼3 nm and lateral dimensions ranging from 20 to 1000 nm. The self-organization is induced by fast cation extraction, leading to attractive dipolar interactions between the NCs. Primary amines play a crucial role in the formation of the CIS NSs, both by forming <i>in situ</i> the cation extracting agent, and by preventing the attachment of NCs to the top and bottom facets of the NSs. Moreover, DFT calculations reveal that the amines are essential to stabilize the covellite crystal structure of the product CIS NSs. The NSs are indium-deficient and the off-stoichiometry gives rise to a plasmon resonance in the NIR spectral window

Room-Temperature Interconversion Between Ultrathin CdTe Magic-Size Nanowires Induced by Ligand Shell Dynamics

The formation mechanisms of colloidal magic-size semiconductor nanostructures have remained obscure. Herein, we report the room temperature synthesis of three species of ultrathin CdTe magic-size nanowires (MSNWs) with diameters of 0.7 ± 0.1 nm, 0.9 ± 0.2 nm, and 1.1 ± 0.2 nm, and lowest energy exciton transitions at 373, 418, and 450 nm, respectively. The MSNWs are obtained from Cd(oleate)2 and TOP-Te, provided diphenylphosphine and a primary alkylamine (RNH2) are present at sufficiently high concentrations, and exhibit sequential, discontinuous growth. The population of each MSNW species is entirely determined by the RNH2 concentration [RNH2] so that single species are only obtained at specific concentrations, while mixtures are obtained at concentrations intermediate between the specific ones. Moreover, the MSNWs remain responsive to [RNH2], interconverting from thinner to thicker upon [RNH2] decrease and from thicker to thinner upon [RNH2] increase. Our results allow us to propose a mechanism for the formation and interconversion of CdTe MSNWs and demonstrate that primary alkylamines play crucial roles in all four elementary kinetic steps (viz., monomer formation, nucleation, growth in length, and interconversion between species), thus being the decisive element in the creation of a reaction pathway that leads exclusively to CdTe MSNWs. The insights provided by our work thus contribute toward unravelling the mechanisms behind the formation of shape-controlled and atomically precise magic-size semiconductor nanostructures

Tailoring ZnSe–CdSe Colloidal Quantum Dots <i>via</i> Cation Exchange: From Core/Shell to Alloy Nanocrystals

We report a study of Zn²⁺ by Cd²⁺ cation exchange (CE) in colloidal ZnSe nanocrystals (NCs). Our results reveal that CE in ZnSe NCs is a thermally activated isotropic process. The CE efficiency (<i>i.e</i>., fraction of Cd²⁺ ions originally in solution, Cd_sol, that is incorporated in the ZnSe NC) increases with temperature and depends also on the Cd_sol/ZnSe ratio. Interestingly, the reaction temperature can be used as a sensitive parameter to tailor both the composition and the elemental distribution profile of the product (Zn,Cd)Se NCs. At 150 °C ZnSe/CdSe core/shell hetero-NCs (HNCs) are obtained, while higher temperatures (200 and 220 °C) produce (Zn_1–<i>x</i>Cd_<i>x</i>)Se gradient alloy NCs, with increasingly smoother gradients as the temperature increases, until homogeneous alloy NCs are obtained at <i>T</i> ≥ 240 °C. Remarkably, sequential heating (150 °C followed by 220 °C) leads to ZnSe/CdSe core/shell HNCs with thicker shells, rather than (Zn_1–<i>x</i>Cd_<i>x</i>)Se gradient alloy NCs. Thermal treatment at 250 °C converts the ZnSe/CdSe core/shell HNCs into (Zn_1–<i>x</i>Cd_<i>x</i>)Se homogeneous alloy NCs, while preserving the NC shape. A mechanism for the cation exchange in ZnSe NCs is proposed, in which fast CE takes place at the NC surface, and is followed by relatively slower thermally activated solid-state cation diffusion, which is mediated by Frenkel defects. The findings presented here demonstrate that cation exchange in colloidal ZnSe NCs provides a very sensitive tool to tailor the nature and localization regime of the electron and hole wave functions and the optoelectronic properties of colloidal ZnSe–CdSe NCs

Anisotropic 2D Cu_2–<i>x</i>Se Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe₂ Nanoparticles

We present the synthesis of colloidal anisotropic Cu_2–<i>x</i>Se nanocrystals (NCs) with excellent size and shape control, using the unexplored phosphine-free selenium precursor 1-dodecaneselenol (DDSe). This precursor forms lamellar complexes with Cu­(I) that enable tailoring the NC morphology from 0D polyhedral to highly anisotropic 2D shapes. The Cu_2–<i>x</i>Se NCs are subsequently used as templates in postsynthetic cation exchange reactions, through which they are successfully converted to CdSe and CuInSe₂ quantum dots, nanoplatelets, and ultrathin nanosheets. The shape of the template hexagonal nanoplatelets is preserved during the cation exchange reaction, despite a substantial reorganization of the anionic sublattice, which leads to conversion of the tetragonal umangite crystal structure of the parent Cu_2–<i>x</i>Se NCs into hexagonal wurtzite CdSe and CuInSe₂, accompanied by a change of both the thickness and the lateral dimensions of the nanoplatelets. The crystallographic transformation and reconstruction of the product NCs are attributed to a combination of the unit cell dimensionalities of the parent and product crystal phases and an internal ripening process. This work provides novel tools for the rational design of shape-controlled colloidal anisotropic Cu_2–<i>x</i>Se NCs, which, besides their promising optoelectronic properties, also constitute a new family of cation exchange templates for the synthesis of shape-controlled NCs of wurtzite CdSe, CuInSe₂, and other metal selenides that cannot be attained through direct synthesis approaches. Moreover, the insights provided here are likely applicable also to the direct synthesis of shape-controlled NCs of other metal selenides, since DDSe may be able to form lamellar complexes with several other metals

Interplay between Surface Chemistry, Precursor Reactivity, and Temperature Determines Outcome of ZnS Shelling Reactions on CuInS₂ Nanocrystals

ZnS shelling of I–III–VI₂ nanocrystals (NCs) invariably leads to blue-shifts in both the absorption and photoluminescence spectra. These observations imply that the outcome of ZnS shelling reactions on I–III–VI₂ colloidal NCs results from a complex interplay between several processes taking place in solution, at the surface of, and within the seed NC. However, a fundamental understanding of the factors determining the balance between these different processes is still lacking. In this work, we address this need by investigating the impact of precursor reactivity, reaction temperature, and surface chemistry (due to the washing procedure) on the outcome of ZnS shelling reactions on CuInS₂ NCs using a seeded growth approach. We demonstrate that low reaction temperatures (150 °C) favor etching, cation exchange, and alloying regardless of the precursors used. Heteroepitaxial shell overgrowth becomes the dominant process only if reactive S- and Zn-precursors (S-ODE/OLAM and ZnI₂) and high reaction temperatures (210 °C) are used, although a certain degree of heterointerfacial alloying still occurs. Remarkably, the presence of residual acetate at the surface of CIS seed NCs washed with ethanol is shown to facilitate heteroepitaxial shell overgrowth, yielding for the first time CIS/ZnS core/shell NCs displaying red-shifted absorption spectra, in agreement with the spectral shifts expected for a type-I band alignment. The insights provided by this work pave the way toward the design of improved synthesis strategies to CIS/ZnS core/shell and alloy NCs with tailored elemental distribution profiles, allowing precise tuning of the optoelectronic properties of the resulting materials

Self-Assembly of Colloidal Hexagonal Bipyramid- and Bifrustum-Shaped ZnS Nanocrystals into Two-Dimensional Superstructures

We present a combined experimental, theoretical, and simulation study on the self-assembly of colloidal hexagonal bipyramid- and hexagonal bifrustum-shaped ZnS nanocrystals (NCs) into two-dimensional superlattices. The simulated NC superstructures are in good agreement with the experimental ones. This shows that the self-assembly process is primarily driven by minimization of the interfacial free-energies and maximization of the packing density. Our study shows that a small truncation of the hexagonal bipyramids is sufficient to change the symmetry of the resulting superlattice from hexagonal to tetragonal, highlighting the crucial importance of precise shape control in the fabrication of functional metamaterials by self-assembly of colloidal NCs

Luminescent CuInS₂ Quantum Dots by Partial Cation Exchange in Cu_2–<i>x</i>S Nanocrystals

Here, we show successful partial cation exchange reactions in Cu_2–<i>x</i>S nanocrystals (NCs) yielding luminescent CuInS₂ (CIS) NCs. Our approach of mild reaction conditions ensures slow Cu extraction rates, which results in a balance with the slow In incorporation rate. With this method, we obtain CIS NCs with photoluminescence (PL) far in the near-infrared (NIR), which cannot be directly synthesized by currently available synthesis protocols. We discuss the factors that favor partial, self-limited cation exchange from Cu_2–<i>x</i>S to CIS NCs, rather than complete cation exchange to In₂S₃. The product CIS NCs have the wurtzite crystal structure, which is understood in terms of conservation of the hexagonal close packing of the anionic sublattice of the parent NCs into the product NCs. These results are an important step toward the design of CIS NCs with sizes and shapes that are not attainable by direct synthesis protocols and may thus impact a number of potential applications

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