Hong-Tao Sun

Luminescent metal nanoclusters: controlled synthesis and functional applications

Abstract Luminescent metal nanoclusters that consist of only several, to tens of, metal atoms and which possess sizes comparable to the Fermi wavelength of electrons have recently attracted significant attention. This new class of luminescent materials not only provides the missing link between atomic and nanoparticle behaviors in metals but also they present abundant novel information for the development of new applicable material systems to meet urgent needs in many areas (such as ultrasensitive sensors for heavy metals, bioimaging, as well as information technology) mainly because of their attractive characteristics, including ultra-small size, good dispersibility, excellent biocompatibility and photostability. In this review, we summarize recent advances in the controlled synthesis and application of luminescent metal nanoclusters, with a particular emphasis on Pt, Mo, Bi and alloy clusters. We also speculate on their future and discuss potential developments for their use in sensors, bioimaging and energy harvesting and conversion.

Ultrabroad near-infrared photoluminescence from Bi5(AlCl4)3 crystal

The Bi5(AlCl4)3 crystal, synthesized by a environmentally friendly room-temperature method using ionic liquids as reaction solvents, exhibits extremely broad near-infrared photoluminescence (PL) with a full width at the half maximum (FWHM) of >510 nm and an effective PL lifetime of 4.1 µs at 1160 nm. We envision that this study not only extends the understanding of photophysical properties of materials containing subvalent bismuth, but also may have promise for the design of novel photonic materials containing a wide array of p-block elements.

Highly Fluorescent Silica‐Coated Bismuth‐Doped Aluminosilicate Nanoparticles for Near‐Infrared Bioimaging

For in vivo and deep-tissue imaging, near-infrared (NIR)-emitting nanoparticles (NPs) offer many advantages over visible-light-emitting NPs because the optical absorption and light scattering of biological media and tissue autofl uores-cence are minimal in the NIR region of the electromagnetic spectrum.

Ultrabroad near-infrared photoluminescence from ionic liquids containing subvalent bismuth

We have shown that Lewis-acidic halogenoaluminate ionic liquid (IL) containing subvalent bismuth can be used as a near-IR (NIR) luminescent material. Raman and absorption spectra evidence the coexistence of Bi(5)(3+) and Bi(+) in the liquid. The Bi(5)(3+) and Bi(+) emitters, stabilized by this Lewis-acidic liquid, demonstrate ultrabroad NIR photoluminescence with a lifetime of around 1 μs. We envisage that the bismuth activated ILs would not only enrich the well-established spectrum of soft luminescent materials but also might promote the design of novel photonic materials activated by other p-block elements.

Synchrotron X-ray, Photoluminescence, and Quantum Chemistry Studies of Bismuth-Embedded Dehydrated Zeolite Y

For the first time, direct experimental evidence of the formation of monovalent Bi (i.e., Bi(+)) in zeolite Y is provided based on the analysis of high-resolution synchrotron powder X-ray diffraction data. Photoluminescence results as well as quantum chemistry calculations suggest that the substructures of Bi(+) in the sodalite cages contribute to the ultrabroad near-infrared emission. These results not only enrich the well-established spectrum of optically active zeolites and deepen the understanding of bismuth related photophysical behaviors, but also may raise new possibilities for the design and synthesis of novel hybrid nanoporous photonic materials activated by other heavier p-block elements.

Efficient Dual-Modal NIR-to-NIR Emission of Rare Earth Ions Co-doped Nanocrystals for Biological Fluorescence Imaging.

A novel approach has been developed for the realization of efficient near-infrared to near-infrared (NIR-to-NIR) upconversion and down-shifting emission in nanophosphors. The efficient dual-modal NIR-to-NIR emission is realized in a β-NaGdF4/Nd(3+)@NaGdF4/Tm(3+)-Yb(3+) core-shell nanocrystal by careful control of the identity and concentration of the doped rare earth (RE) ion species and by manipulation of the spatial distributions of these RE ions. The photoluminescence results reveal that the emission efficiency increases at least 2-fold when comparing the materials synthesized in this study with those synthesized through traditional approaches. Hence, these core-shell structured nanocrystals with novel excitation and emission behaviors enable us to obtain tissue fluorescence imaging by detecting the upconverted and down-shifted photoluminescence from Tm(3+) and Nd(3+) ions, respectively. The reported approach thus provides a new route for the realization of high-yield emission from RE ion doped nanocrystals, which could prove to be useful for the design of optical materials containing other optically active centers.

Superbroadband near-IR nano-optical source based on bismuth-doped high-silica nanocrystalline zeolites.

We have shown that efficient superbroadband near-IR luminescence can be realized in bismuth-doped high-silica nanocrystalline zeolites. The emission band covered the range of 930-1620 nm, with a maximum peak at 1146.3 nm, an FWHM of 152 nm, and a lifetime of over 300 mus under the excitation of a 488 nm laser line. The observed luminescence was attributed to subvalent Bi (Bi(+)) ions formed in the annealed zeolites. These Bi-doped nanozeolites may find applications as superbroadband near-IR nano-optical sources.

Experimental and theoretical studies of photoluminescence from Bi82+ and Bi53+ stabilized by [AlCl4]− in molecular crystals

The photophysical properties of Bi82+ and Bi53+ polycations stabilized by [AlCl4]− have been studied experimentally and theoretically. The obtained product was thoroughly evaluated by powder X-ray diffraction and photoluminescence spectroscopy, making it clear that both Bi82+ and Bi53+ contribute to the observed broad near-infrared emission. Furthermore, it was revealed that the Bi82+ polycation shows emission peaking at ca. 1180 nm, while Bi53+ shows the longer-wavelength emission. The following quantum chemistry calculation on the Bi82+ polycation helps us attribute some of the observed excitation bands in the visible spectral range to specific electronic transitions of bismuth polycations. It is believed that systematic investigation of structural and luminescent properties as well as detailed quantum chemistry calculation of molecular crystals containing such kinds of bismuth units allows us to obtain a clearer picture of bismuth-related photophysical behaviors, which not only serve to solve the confusions on the luminescence origin of bismuth in other material systems such as bulk glasses, glass fibers and conventional crystals, but also is helpful to develop novel applicable broadband tunable laser mediums.

Spectroscopic characterization of bismuth embedded Y zeolites

Bismuth embedded Y zeolites were studied by using UV-vis- near infrared (NIR) diffuse reflectance, Raman, and steady-state NIR photoluminescence spectroscopy. The results suggest that Bi53+ and Bi+ active centers coexist in the dehydrated and hydrated zeolite framework, both of which contribute to NIR emission. Furthermore, it was revealed that the high-temperature annealing leads to the formation of Bi2O3 clusters, which act as blocks for selectively closing down the “in-out windows” of H2O and O2 molecules in the zeolites. It is believed that these materials can find a wide array of applications as active media of broadly tunable micro or nano-optical sources.

Efficient near-infrared luminescence and energy transfer in erbium/bismuth codoped zeolites

We have shown that tunable and highly efficient broadband near-IR (NIR) luminescence can be realized in erbium/bismuth codoped zeolites. The emission covers the ranges of 930-1450nm and 1450-1630nm. The intensity ratio of the two bands can be tuned by adjusting the concentration of erbium and the excitation wavelength. Steady-state and time-resolved photoluminescence (PL), and PL excitation measurements indicate that two kinds of emitters coexist in the pores of zeolites, and that NIR active bismuth simultaneously acts as a sensitizer of erbium. The present results demonstrate an important rational strategy for the design of a tunable NIR-emitting zeolite-based nanosystem.