Stimulated blue emission in reconstituted films of ultrasmall silicon nanoparticles

We dispersed electrochemical etched Si into a colloid of ultrabright blue luminescent nanoparticles (1 nm in diameter) and reconstituted it into films or microcrystallites. When the film is excited by a near-infrared two-photon process at 780 nm, the emission exhibits a sharp threshold near 106 W/cm2, rising by many orders of magnitude, beyond which a low power dependence sets in. Under some conditions, spontaneous recrystallization forms crystals of smooth shape from which we observe collimated beam emission, pointing to very large gain coefficients. The results are discussed in terms of population inversion, produced by quantum tunneling or/and thermal activation, and stimulated emission in the quantum confinement-engineered Si-Si phase found only on ultrasmall Si nanoparticles. The Si-Si phase model provides gain coefficients as large as 103-105 cm-1. © 2001 American Institute of Physics

Uptake and toxicity studies of poly-acrylic acid functionalized silicon nanoparticles in cultured mammalian cells

Poly-acrylic acid (PAAc) terminated silicon nanoparticles (SiNPs) have been synthesized and employed as a synchronous fluorescent signal indicator in a series of cultured mammalian cells: HHL5, HepG2 and 3T3-L1. Their biological effects on cell growth and proliferation in both human and mouse cell lines have been studied. There was no evidence of in vitro cytotoxity in the cells exposed to PAAc terminated SiNPS when assessed by cell morphology, cell proliferation and viability, and DNA damage assays. The uptake of the nanocrystals by both HepG2 and 3T3-L1 cells was investigated by confocal microscopy and flow cytometry, which showed a clear time-dependence at higher concentrations. Reconstructed 3-D confocal microscope images exhibited that the PAAc-SiNPs were evenly distributed throughout the cytosol rather than attached to outer membrane. This study provides fundamental evidence for the safe application and further modification of silicon nanoparticles, which could broaden their application as cell markers in living systems and in micelle encapsulated drug delivery systems

Second harmonic generation in microcrystallite films of ultrasmall Si nanoparticles

We dispersed crystalline Si into a colloid of ultrasmall nano particles (∼1 nm), and reconstituted it into microcrystallites films on device-quality Si. The film is excited by near-infrared femtosecond two-photon process in the range 765-835 nm, with incident average power in the range 15-70 mW, focused to ∼1 μm. We have observed strong radiation at half the wavelength of the incident beam. The results are analyzed in terms of second-harmonic generation, a process that is not allowed in silicon due to the centrosymmetry. Ionic vibration of or/and excitonic self-trapping on novel radiative Si-Si dimer phase, found only in ultrasmall nanoparticles, are suggested as a basic mechanism for inducing anharmonicity that breaks the centrosymmetry. © 2000 American Institute of Physics

Biocompatible fluorescent silicon nanocrystals for single-molecule tracking and fluorescence imaging.

Fluorescence microscopy is used extensively in cell-biological and biomedical research, but it is often plagued by three major problems with the presently available fluorescent probes: photobleaching, blinking, and large size. We have addressed these problems, with special attention to single-molecule imaging, by developing biocompatible, red-emitting silicon nanocrystals (SiNCs) with a 4.1-nm hydrodynamic diameter. Methods for producing SiNCs by simple chemical etching, for hydrophilically coating them, and for conjugating them to biomolecules precisely at a 1:1 ratio have been developed. Single SiNCs neither blinked nor photobleached during a 300-min overall period observed at video rate. Single receptor molecules in the plasma membrane of living cells (using transferrin receptor) were imaged for ≥10 times longer than with other probes, making it possible for the first time to observe the internalization process of receptor molecules at the single-molecule level. Spatial variations of molecular diffusivity in the scale of 1-2 µm, i.e., a higher level of domain mosaicism in the plasma membrane, were revealed

Effect of size and surface structure manipulation on the luminescent properties of silicon nanoclusters

Structures measuring several nanometers in any dimension represent a transitional scale between materials with crystalline order and molecules. Quantum confinement of the carrier wavefunction within such structures may significantly alter their electronic behavior. Additionally, the effect of surface reconstruction becomes substantial at this scale. This work investigated electronic and structural properties of silicon nanoclusters. Electrochemical etching was used to produce particles smaller than 3 nm in diameter. Electron microscopy and material analysis studies showed the particles to have a crystalline silicon core with significant structural reconstruction on the surface. Also, the clusters were found to be spherical in shape and quantized in size below 3 nm in diameter. The efficient luminescence of the material was studied and interpreted through the existing luminescence models. Surface modifications leading to functionalization were carried out. Both structural and luminescent characteristics of the modified clusters were studied, revealing a weak dependence of the luminescence efficiency on exchanging the surface hydrogen atoms for other single bonded species. The observed optical activity of silicon nanoclusters makes them an important material for a variety of scientific applications.U of I Onlythesis/dissertatio