Jiyang Fan

Group IV Nanoparticles: Synthesis, Properties, and Biological Applications

In this review, the emerging roles of group IV nanoparticles including silicon, diamond, silicon carbide, and germanium are summarized and discussed from the perspective of biologists, engineers, and medical practitioners. The synthesis, properties, and biological applications of these new nanomaterials have attracted great interest in the past few years. They have gradually evolved into promising biomaterials due to their innate biocompatibility; toxic ions are not released when they are used in vitro or in vivo, and their wide fluorescence spectral regions span the near-infrared, visible, and near-ultraviolet ranges. Additionally, they generally have good resistance against photobleaching and have lifetimes on the order of nanoseconds to microseconds, which are suitable for bioimaging. Some of the materials possess unique mechanical, chemical, or physical properties, such as ultrachemical and thermal stability, high hardness, high photostability, and no blinking. Recent data have revealed the superiority of these nanoparticles in biological imaging and drug delivery.

Synthesis and low-temperature photoluminescence properties of SnO2 nanowires and nanobelts

Ultra-long rutile tin dioxide nanowires and nanobelts are synthesized by thermal oxidation of tin powder using gold film as the catalyst. Nanowire or nanobelts can be selectively produced by tuning the reaction temperature. The vapour-liquid-solid growth mechanism is proposed. The band gaps of the nanowires and nanobelts are 3.74 and 3.81xa0eV respectively, determined from UV/visible absorption spectral results. The SnO2 nanowires show stable photoluminescence with two emission peaks centred at around 470 and 560xa0nm. Their wavelengths stay almost fixed while their intensities depend sensitively on the temperatures within the examination ranges from 10 to 300xa0K. The SnO2 nanobelts show similar photoluminescence behaviours and the origin of the luminescence is discussed.

3C-SiC nanocrystals as fluorescent biological labels.

Quantum dots are superior to dye molecules in many aspects from size-tunable fluorescence and resistance to photobleaching and they have thus been widely used in biology as fluorescent probes. However, the cytotoxicity of some quantum dots limits their use in biological systems, and exploiting green nanoparticles with low cytotoxicity has become one major concern in this field. Silicon carbide, one well-known power electronic semiconductor material, is considered one of the best biocompatible materials, especially to blood. In addition, it has superior properties such as low density, high hardness, high strength, and chemical inertness. In recent years, much effort has been made to synthesize nanocrystalline SiC and study its photoluminescence (PL) properties. Some synthesized SiC nanostructures showed emission in the blue-to-UV range with their properties depending sensitively on the fabrication method and even on specific experiments. Although some variations have been reported, in general the observed emissions can be ascribed to some surface or defect states in the SiC nanostructures. However, owing to their relatively large size, low emission intensity, lack of controlled synthesis, and variable optical properties, these interconnected SiC nanostructures can hardly be used as fluorescent biological labels. Kassiba and co-workers synthesized SiC nanoparticles with diameters of tens of nanometers

Luminescence from colloidal 3C-SiC nanocrystals in different solvents

We have investigated the role of the solvents in the luminescence from colloidal 3C-SiC suspensions. By dispersing electrochemically etched polycrystalline 3C-SiC wafers in water, ethanol, or toluene, we have fabricated suspensions of 3C-SiC nanocrystals that exhibit intense photoluminescence. By taking into account the quantum confinement effect and observed size distributions of the 3C-SiC crystallites, a simple model is formulated to explain the photoluminescence spectra. Our results show that the colloidal 3C-SiC nanocrystals are robust and intense emitters that have good chemical stability and biocompatibility. They are thus useful in biotechnology and nano-optoelectronics applications.

Red shift in the photoluminescence of colloidal carbon quantum dots induced by photon reabsorption

We synthesize the colloidal carbon/graphene quantum dots 1–9u2009nm in diameter and study their photoluminescence properties. Surprisingly, the luminescence properties of a fixed collection of colloidal carbon quantum dots can be systematically changed as the concentration varies. A model based on photon reabsorption is proposed which explains well the experiment. Infrared spectral study indicates that the surfaces of the carbon quantum dots are substantially terminated by oxygen atoms, which causes their ultra-high hydrophilicity. Our result clarifies the mystery of distinct emission colors in carbon quantum dots and indicates that photon reabsorption can strongly affect the luminescence properties of colloidal nanocrystals.

Luminescent silicon carbide nanocrystallites in 3C-SiC∕polystyrene films

We report optical emission of SiC nanocrystallite films, which clearly shows the quantum confinement effect. Bulk polycrystalline 3C-SiC was first electrochemically etched and then the fabricated porous silicon carbide was ultrasonically treated in water or toluene suspension to disperse into colloidal nanoparticles. Transmission electron microscopy images clearly show that the colloidal nanoparticles have 3C-SiC lattice structure with sizes varying from about 6nm down to below 1nm. The suspension of 3C-SiC nanocrystallites exhibits ultrabright emission with wavelengths ranging from 400to520nm when the excitation wavelength varies from 250to480nm, in accordance with the quantum confinement effect. By adding polystyrene to the toluene suspension containing SiC nanoparticles and coating the mixing solution onto a Si wafer, we obtain the SiC∕polystyrene films that luminesce.

Vacuum electron field emission from SnO2 nanowhiskers annealed in N2 and O2 atmospheres

The field emission properties of SnO2 nanowhiskers were observed to change after annealing under O2 and N2. The electron current increased significantly from the sample annealed in N2 and the threshold field decreased from 3.17V∕μm of the as-grown sample to 2.59V∕μm of the annealed sample. The mechanism of the field emission enhancement was explored using Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy (XPS). The results reveal that after annealing in N2, the amount of Sn–O bonds decreased and N atoms were introduced onto the surface. The binding energies of Sn 3d and O 1s determined by high resolution XPS analysis show a shift of 0.55 and 0.47eV, respectively, toward the high energy side. This shows that the electron emission enhancement arises from a decrease in the work function. The changes in the field emission effect from the sample annealed in O2 are different and a possible mechanism is also proposed.

Excitation and recombination photodynamics in colloidal cubic SiC nanocrystals

We studied the photodynamics of the different-sized colloidal cubic SiC nanocrystals in distinct polar and nonpolar solvents. The UV-visible absorption spectral study indicates that the SiC nanocrystals with an average size of 4 nm retain an indirect energy gap; whereas the smaller quantum dots about 1 nm in size exhibit discrete and sharp absorption features indicating their discrete energy levels and the result agrees well with theoretical results. The colloidal SiC nanocrystals exhibit triple-exponential photoluminescence decay with nanosecond-order lifetimes which show slight size-dependence.

Identification of luminescent surface defect in SiC quantum dots

The surface defect that results in the usually observed blue luminescence in the SiC quantum dots (QDs) remains unclear. We experimentally identify that the surface defect C=O (in COO) is responsible for this constant blue luminescence. The HO···C=O [n(OH) → π*(CO)] interaction between the hydroxyl and carbonyl groups changes the energy levels of C=O and makes the light absorption/emission arise at around 326/438u2009nm. Another surface defect (Si–Si) is identified and its light absorption contributes to both C=O-related luminescence and quantum-confinement luminescence of the SiC QDs.

Highly bright tunable blue-violet photoluminescence in SiC nanocrystal–sodium dodecyl sulfonate crosslinked network

We report strong photoluminescence in an ultra-small surface oxidized SiC quantum dot-sodium dodecyl sulfonate crosslinked network. The peak emission wavelength is tunable spanning a wide blue-violet spectral region showing clear quantum confinement effects. The photoluminescence decay exhibits triple recombination dynamics with an average lifetime of 13.65 ns.