Blue-LED-excitable NIR-II luminescent lanthanide-doped SrS nanoprobes for ratiometric thermal sensing
TL;DR: In this article, a novel NIR-II luminescent nanoprobe based on efficient energy transfer from Ce3+ to Er3+ and Nd3+ in sub-10 nm SrS nanocrystals (NCs) was reported.
Abstract: Lanthanide (Ln3+)-doped near infrared (NIR)-II luminescent nanoprobes have shown great promise in many technological fields, but are currently limited by the low absorption efficiency of Ln3+ due to the forbidden 4f→4f transition. Herein, we report a novel NIR-II luminescent nanoprobe based on efficient energy transfer from Ce3+ to Er3+ and Nd3+ in sub-10 nm SrS nanocrystals (NCs), which are excitable by using a commercial blue light-emitting diode (LED). Through sensitization by the allowed 4f→5d transition of Ce3+, the NCs exhibit strong NIR-II luminescence from Er3+ and Nd3+ with quantum yields of 2.9% and 2.3%, respectively. Furthermore, by utilizing the intense NIR-II luminescence of Er3+ from the thermally coupled Stark sublevels of 4I13/2, we demonstrate the application of SrS:Ce3+/Er3+ NCs as blue-LED-excitable NIR-II luminescent nanoprobes for ratiometric thermal sensing. These findings reveal the unique advantages of SrS:Ln3+ NCs in NIR-II luminescence, which may open up a new avenue for exploring novel and versatile luminescent nanoprobes based on Ln3+-doped sulphide NCs.
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TL;DR: In this paper , a novel strategy based on Te4+/Ln3+ (Ln = Er, Nd, and Yb) co-doping was proposed to achieve efficient NIR luminescence in vacancy-ordered double perovskite Cs2ZrCl6 phosphors, which are excitable by a low-cost near-ultraviolet light-emitting diode (LED) chip.
Abstract: All-inorganic lead-free perovskite-derivative metal halides have shown great promise in optoelectronics, however, it remains challenging to realize efficient near-infrared (NIR) luminescence in these materials. Herein, we report a novel strategy based on Te4+/Ln3+ (Ln = Er, Nd, and Yb) co-doping to achieve efficient NIR luminescence in vacancy-ordered double perovskite Cs2ZrCl6 phosphors, which are excitable by a low-cost near-ultraviolet light-emitting diode (LED) chip. Through sensitization by the spin-orbital allowed 1S0 → 3P1 transition of Te4+, intense and multi-wavelength NIR luminescence originating from the 4f → 4f transitions of Er3+, Nd3+, and Yb3+ was acquired, with a quantum yield of 6.1% for the Er3+ emission. These findings provide a general approach to achieve efficient NIR emission in lead-free metal halides through ns2-metal and lanthanide ion co-doping, thereby opening up a new avenue for exploring NIR-emitting perovskite derivatives towards versatile applications such as NIR-LEDs and bioimaging.
27 citations
TL;DR: In this paper , a series of Ln3+-doped BiF3 sub-microparticles were synthesized through microwave assisted synthesis and the effects of doping were evaluated from the structural and morphological viewpoint.
Abstract: The design of molecular materials suitable for disparate fields could lead to new advances in engineering applications. In this work, a series of Ln3+-doped BiF3 sub-microparticles were synthesized through microwave-assisted synthesis. The effects of doping are evaluated from the structural and morphological viewpoint. In general, increasing the Ln3+ concentration the octahedral habitus is distorted to a spheric one, and some aggregates are visible without any differences in the crystalline phase. The optical response of the samples confirms that the BiF3 materials are suitable hosts for the luminescence of the tested trivalent lanthanide (Ln3+) ions (Ln = Eu, Tb, Tm, Ho, Er, Yb). A Yb3+/Er3+ co-doped sample is presented as an illustrative example of all-photonic molecular logic operations and primary luminescent thermometry.
4 citations
TL;DR: In this paper , the authors describe the colloidal synthesis of alkaline-earth chalcogenide nanocrystals through the reaction of metal carboxylates with carbon disulfide or selenourea.
Abstract: Increasing demand for effective energy conversion materials and devices has renewed interest in semiconductors comprised of earth-abundant and biocompatible elements. Alkaline-earth sulfides doped with rare earth ions are versatile optical materials. However, relatively little is known about controlling the dimensionality, surface chemistry, and inherent optical properties of the undoped versions of alkaline-earth mono- and polychalcogenides. We describe the colloidal synthesis of alkaline-earth chalcogenide nanocrystals through the reaction of metal carboxylates with carbon disulfide or selenourea. Systematic exploration of the synthetic phase space allows us to tune particle sizes over a wide range using a mixture of commercially available carboxylate precursors. Solid-state NMR spectroscopy confirms the phase purity of the selenide compositions. Surface characterization reveals that bridging carboxylates and amines preferentially terminate the surface of the nanocrystals. While these materials are colloidally stable in the mother solution, the selenides are susceptible to oxidation over time, eventually degrading to selenium metal through polyselenide intermediates. As part of these investigations, we have developed the colloidal syntheses of barium di- and triselenides, two among few reported nanocrystalline alkaline-earth polychalcogenides. Electronic structure calculations reveal that both materials are indirect band gap semiconductors. The colloidal chemistry presented here may enable the synthesis of more complex, multinary chalcogenide materials containing alkaline-earth elements.
4 citations
TL;DR: In this article , a novel strategy based on Te4+/Ln3+ (Ln=Er, Nd, and Yb) co-doping was proposed to achieve efficient NIR luminescence in vacancy-ordered double perovskite Cs2ZrCl6 phosphors, which are excitable by a low-cost near-ultraviolet light-emitting diode (LED) chip.
Abstract: All-inorganic lead-free perovskite-derivative metal halides have shown great promise in optoelectronics, however, it remains challenging to realize efficient near-infrared (NIR) luminescence in these materials. Herein, we report a novel strategy based on Te4+/Ln3+ (Ln=Er, Nd, and Yb) co-doping to achieve efficient NIR luminescence in vacancy-ordered double perovskite Cs2ZrCl6 phosphors, which are excitable by a low-cost near-ultraviolet light-emitting diode (LED) chip. Through sensitization by the spin-orbital allowed 1S0→3P1 transition of Te4+, intense and multi-wavelength NIR luminescence originating from the 4f→4f transitions of Er3+, Nd3+, and Yb3+ was acquired, with a quantum yield of 6.1 % for the Er3+ emission. These findings provide a general approach to achieve efficient NIR emission in lead-free metal halides through ns2-metal and lanthanide ion co-doping, thereby opening up a new avenue for exploring NIR-emitting perovskite derivatives towards versatile applications such as NIR-LEDs and bioimaging.
4 citations
TL;DR: In this article , two new lanthanide mercury isonicotinic acid complexes [Sm(IA)3(H2O)2]2n2n(HgCl4)·3nCl·7nH3O·2nH 2O (1; IA = isonic-acid anion) and [Gd(IA),3(h3O),2] 2nHg3Br8]n(n HgBr2)· 2nNO3 (2; IA= isonic acid anion), were synthesized.
3 citations
References
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TL;DR: In this paper, a unified treatment for phonon sideband intensities, multiphonon relaxation transition probabilities, and phonon-assisted energy-transfer probabilities is given in the adiabatic approximation.
Abstract: A unified treatment is given in the adiabatic approximation for phonon sideband intensities, multiphonon relaxation transition probabilities, and phonon-assisted energy-transfer probabilities. The intensity distribution of phonon sidebands is determined by coupling constants of the vibrational modes with electrons or holes and a criterion for the appearance of discrete sidebands is given. Transition probabilities of multiphonon relaxation processes among various excited levels of an ion are shown to depend exponentially on the energy gap between these levels, in agreement with recent experimental results. A similar dependence is derived for the energy-transfer probabilities between two ions on the energy mismatch between excitation energies of these ions.
791 citations
575 citations
TL;DR: In this paper, the Huang-Rhys theory of multiphonon emission was used to calculate the radiative and non-radiative rates for five luminescing states in fluorozirconate glass.
Abstract: Optical-absorption, -emission, and -excitation spectra are presented for ${\mathrm{Er}}^{3+}$ ions in fluorozirconate glass. Measured oscillator strengths of the transitions between $J$ manifolds at 300 and 15 K are compared with calculated electric and magnetic dipole oscillator strengths. Radiative rates for five luminescing states were calculated. The nonradiative rates from these excited states were determined by calculating the difference between the measured rates and the calculated radiative rates. The low-temperature nonradiative rates are in agreement with the phenomenological energy-gap law followed by rare-earth ions in a number of crystals and glasses. The temperature dependence of the lifetimes was analyzed using the Huang-Rhys theory of multiphonon emission. Values for the $^{4}I_{\frac{11}{2}}$ radiative and nonradiative rates obtained by the above methods are compared with those obtained applying the method Flaherty and DiBartolo used to study Mn${\mathrm{F}}_{2}$: ${\mathrm{Er}}^{3+}$. The multiphonon emission rates in fluorozirconate glass are much lower than the rates for the same levels of ${\mathrm{Er}}^{3+}$ in oxide glasses. Measurements of the bandwidths of the ground and excited states of ${\mathrm{Er}}^{3+}$ and the nearly exponential decay of the emissions indicate a relatively narrow distribution of site symmetries compared to oxide glasses.
573 citations
TL;DR: A strategy to achieve a ratiometric thermometer by encapsulating luminescent perylene dye into the pores of a europium metal-organic framework (MOF) is developed, which exhibits highly temperature-dependent luminescence intensity ratio over the physiological temperature range.
Abstract: A strategy to achieve a ratiometric thermometer by encapsulating luminescent perylene dye into the pores of a europium metal-organic framework (MOF) is developed. The resulting MOF⊃dye thermometer exhibits highly temperature-dependent luminescence intensity ratio over the physiological temperature range, with a maximum sensitivity of 1.28% °C(-1) at 20 °C.
556 citations
TL;DR: The recent advances of various NIR-II nano-agents (including single-walled carbon nanotubes, quantum dots, rare-earth doped nanoparticles, other inorganic nanomaterials, small organic molecule-based nanoparticles and semiconducting polymer nanoparticles) in both bioimaging and therapeutic applications are summarized.
Abstract: The optical technology presents non-invasive, non-destructive, and non-ionizing features and has the ability to display various chemical components in tissues to provide useful information for various biomedical applications. Regarding selection of light wavelengths, second near-infrared (NIR-II, 900-1700 nm) light is a much better choice compared to both visible (380-780 nm) and traditional near-infrared (780-900 nm) light, because of its advantages including deeper penetration into biological tissues, less tissue scattering or absorption, and decreased interference by fluorescent proteins. Thus, using optical nano-agents that absorb or emit light in the NIR-II window can achieve deeper tissue optical imaging with higher signal-to-background ratios and better spatial resolution for diagnosis. What's more, some of these nano-agents can be further applied for imaging guided surgical removal, real-time monitoring of drug delivery, labeling lymphatic metastasis, biosensing, and imaging guided phototherapy. In this review, we attempt to summarize the recent advances of various NIR-II nano-agents (including single-walled carbon nanotubes, quantum dots, rare-earth doped nanoparticles, other inorganic nanomaterials, small organic molecule-based nanoparticles, and semiconducting polymer nanoparticles) in both bioimaging and therapeutic applications, and discuss the challenges and perspectives of these nano-agents for clinical practice in the near future.
364 citations