Encapsulation of InP/ZnS Quantum Dots into MOF-5 Matrices for Solid-State Luminescence: Ship in the Bottle and Bottle around the Ship Methodologies
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PROVIDER: S-EPMC11242582 | biostudies-literature | 2024 Jun
REPOSITORIES: biostudies-literature
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Project description:In this work, we report the synthesis of high-quality, nontoxic InP/ZnS core-shell quantum dots (QDs). The temperature-dependent optical properties such as photoluminescence (PL), absorption, and PL decay with time have been investigated. Based on the temperature dependence of optical properties of QDs, three different configurations of temperature sensors using PMMA as the QD host material were fabricated. The temperature sensor configurations are planar thin-film (InP/ZnS QD)/PMMA deposited on a Si wafer (sensor 1), (InP/ZnS QD)/PMMA-filled borosilicate fibers (sensor 2), and InP/ZnS QD-doped electrospun PMMA nanofibers deposited on a Si wafer (sensor 3). After fabrication, the performance of the temperature sensors have been thoroughly investigated through photoluminescence reversibility tests in consecutive heating-cooling cycles, and the sensitivity of the sensors has been calculated. The three sensors have shown different critical reversible temperatures above which they go through irreversible structural damage and lose their reversibility. The highest critical reversible temperature of 95 °C and the highest sensitivity of 2.1% °C-1 have been achieved, which are comparable to Cd- and dye-based temperature sensors reported to date. The sensors were found to be highly stable, which demonstrated negligible degradation even after 30 days of exposure to ambient conditions. The InP/ZnS QD-based optical temperature sensors can be considered to be a potential replacement for toxic heavy-metal QD-based optical temperature sensors.
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Project description:Traditionally, ZnS or ZnSe is chosen as the shell material for InP quantum dots (QDs). However, for green or blue InP QDs, the ZnSe shell will form a type-II structure resulting in a redshift of the emission spectrum. Although the band gap of ZnS is wider, its lattice mismatch with InP is larger (∼7.7%), resulting in more defect states and lowered quantum yield (QY). To overcome the above problems, we introduced the intermediate ZnMnS layer in InP/ZnMnS/ZnS QDs. The wide band gap of the intermediate layer (3.7 eV) can confine the electrons and holes in the core completely, and the formation of the type-II structure is avoided. As a result, green InP-based QDs with QY up to 80% were obtained. By adjusting the halogen ratios of the ZnX2 precursor, the minimum and maximum emission peaks are 470 and 620 nm, respectively, covering the whole visible range. Finally, after optimizing the coating shell process, the maximum external quantum efficiency of QD light-emitting diodes fabricated from this InP-based green light QDs can reach 2.7%.
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Project description:Highly pure millimeter-sized MOF-5 single crystals were synthesized and characterized. Photoluminescence (PL) spectroscopy and time-correlated single photon counting (TCSPC) demonstrate a solvent-guest dependency of MOF-5 emission and its ligand-centred nature. These results allow measuring the true MOF-5 luminescence free of solvent at a wavelength of 355 nm, a significantly lower wavelength than previously published. MOF-5 emission was also evaluated with different solvents and various degrees of water intake, explaining previously published observations. Comparison between lifetimes shows the fluorophore stabilization within the frameworks and demonstrates the progressive influence of the Zn4O subunits on the fluorescence during hydration. Overall, this work highlights the necessity to obtain phase-pure material, especially when moisture sensitivity can play a role, before ascribing electronic transitions. This study is a rigorous new take on the iconic MOF-5 and on its photoluminescence properties.
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Project description:Macroscopic scale sources of polarized light play a fundamental role in designing light-emitting devices. In this communication we report the formation of nano- and macro-scale ordered, layered assemblies of InP/ZnS quantum dots (QDs) exhibiting fluorescence anisotropy (FA), as well as thermo- and mechano-responsive properties. The long-range organization of small, quasi-isotropic nanoparticles was achieved by introducing liquid crystal molecules to the surface of QDs, without the need to use an organic matrix. Melting/crystallization of the ligand at 95 deg. C translated to a reversible reconfiguration of QDs thin film between 2D layered and body-centered cubic structures, characteristic for a temperature range below and above the melting point, respectively. The low-temperature, layered structure exhibited mechano-responsiveness which was key to introduce and control the sample alignment. Interestingly, transverse and parallel alignment modes of QDs layers were achieved, depending on the temperature of mechanical shearing. As prepared QD samples exhibited fluorescence anisotropy strongly correlated to the macroscopic orientation of the layers. Correlated small-angle X-ray diffraction (SAXRD) and fluorescence spectroscopy studies confirmed the mm-scale alignment of the thin films of QDs. Such films may be advantageous for developing efficient, densely packed, and uniform macro-scale FA sources.
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Project description:Silicene or the two-dimensional (2D) graphene-like silicon allotrope has recently emerged as a promising candidate for various applications in nanotechnology. However, concerns on the silicene stability still persist to date and need to be addressed aiming at the fabrication of competing and durable silicene-based devices. Here, we present an all-around encapsulation methodology beyond the current state-of-the-art silicene configuration, namely silicene sandwiched in between a capping layer (e.g., Al2O3) and the supporting substrate (e.g., Ag). In this framework, the insertion of one or two sacrificial 2D Sn layers enables the realization of different atomically thin encapsulation schemes, preserving the pristine properties of silicene while decoupling it from the growth template. On one hand, the epitaxy of a 2D Sn layer before silicene allows for the removal of the Ag substrate with no effect on silicene which in turn can be easily gated, for example, with an oxide layer on its top face. On the other hand, a full 2D encapsulation scheme, where top and bottom faces of silicene are protected by 2D Sn layers, gives rise to an atomically thin and cm2-scaled membrane preventing degradation of silicene for months. Both schemes thus constitute an advancement for the silicene stability and encapsulation in ambient conditions, paving the way to further exploitation in flexible electronics and photonics.
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