Jeffrey R. DiMaio

White light emissions through down-conversion of rare-earth doped LaF 3 nanoparticles

Through the use of complex core-shell structures, white light emissions are observed from a single nanoparticle doped with multiple trivalent rare-earth ions. The internal structuring of the nanoparticle to allow for a controlled degree of energy transfer a common excitation wavelength yielding the white light emission is obtained. Emissions with correlated color temperatures ranging from 2700K to 5000K were produced. The stability of the phosphors to excitation wavelength variations was examined.

Controlling energy transfer between multiple dopants within a single nanoparticle

Complex core-shell architectures are implemented within LaF3 nanoparticles to allow for a tailored degree of energy transfer (ET) between different rare earth dopants. By constraining specific dopants to individual shells, their relative distance to one another can be carefully controlled. Core-shell LaF3 nanoparticles doped with Tb3+ and Eu3+ and consisting of up to four layers were synthesized with an outer diameter of ≈10 nm. It is found that by varying the thicknesses of an undoped layer between a Tb3+-doped layer and a Eu3+-doped layer, the degree of ET can be engineered to allow for zero, partial, or total ET from a donor ion to an acceptor ion. More specifically, the ratio of the intensities of the 541-nm Tb3+ and 590 nm Eu3+ peaks was tailored from <0.2 to ≈2.4 without changing the overall composition of the particles but only by changing the internal structure. Further, the emission spectrum of a blend of singly doped nanoparticles is shown to be equivalent to the spectra of co-doped particles when a core-shell configuration that restricts ET is used. Beyond simply controlling ET, which can be limiting when designing materials for optical applications, this approach can be used to obtain truly engineered spectral features from nanoparticles and composites made from them. Further, it allows for a single excitation source to yield multiple discrete emissions from numerous lanthanide dopants that heretofore would have been quenched in a more conventional active optical material.

Color kinetic nanoparticles.

Eu3+ doped LaF3 nanoparticles functionalized with a 3-4 formylphenyl benzoic acid ligand were synthesized. Excitation energy-dependent energy transfer from the ligand to Eu3+ yields color tunability from the red to greenish-blue as a function of excitation wavelengths. This synthetic approach provides large shifts in the resultant chromaticity with an excitation wavelength including the generation of white light.

Preparation and Characterization of Rare Earth Doped Fluoride Nanoparticles

This paper reviews the synthesis, structure and applications of metal fluoride nanoparticles, with particular focus on rare earth (RE) doped fluoride nanoparticles obtained by our research group. Nanoparticles were produced by precipitation methods using the ligand ammonium di-n-octadecyldithiophosphate (ADDP) that allows the growth of shells around a core particle while simultaneously avoiding particle aggregation. Nanoparticles were characterized on their structure, morphology, and luminescent properties. We discuss the synthesis, properties, and application of heavy metal fluorides; specifically LaF3:RE and PbF2, and group IIA fluorides. Particular attention is given to the synthesis of core/shell nanoparticles, including selectively RE-doped LaF3/LaF3, and CaF2/CaF2 core/(multi-)shell nanoparticles, and the CaF2-LaF3 system.

Transparent silica glasses containing single walled carbon nanotubes

Organic/inorganic matrix nanocomposites have been created using an acid catalyzed, tetraethyl orthosilicate-based sol-gel technique with single-walled carbon nanotubes (SWNTs). By utilizing nanotubes functionalized with the dendron methyl 3,5-di(methyltrigycoloxy)benzylic alcohol (IPEG), ultrasonic blending in the sol phase prior to gelation yields excellent dispersion characteristics of the nanotube phase. The glasses were densified by heating to 600 °C yielding 80% of theoretical density with little change in the optical appearance or behavior. These materials exhibited intrinsic Rayleigh scattering, suggesting near ideal dispersion. Nonlinear optical transmission was observed for 1064 and 532 nm light suggesting that the matrix has a strong broad band coupling to the optical field. Such composites allow for a host of applications based on the novel confinement properties of carbon nanotubes in a robust inorganic host.

Polarization-dependent transmission through subwavelength anisotropic aperture arrays

The use of polarized light as an approach to further control the extraordinary transmission (EOT) through nanostructured metallic films has recently gained attention. In this work, it is shown that aperture shape and orientation not only determine the intensity of the polarized light emitted, corroborating the previous work of others, but also can be used to spectrally tune the relative peak intensity of surface plasmon polaritons modes. The high extinction ratio of high aspect ratio apertures lends itself to the creation of micron sized structures that emit at different wavelengths depending upon the orientation of linearly polarized incident light. This has many potential applications including the prospect of color shifting pixels for high definition television (HDTV) and thin film electroluminescent (TFEL) devices as well as novel polarization mode dispersion control components.

Photonic band engineering through tailored microstructural order

Colloidal solids of monosized, solution-derived SiO2 were prepared under forced and unforced sedimentation conditions to tailor the level of particulate order. Photonic band gaps were observed in the blue part of the visible spectrum and their spectral shape is shown experimentally to correlate directly to the degree of long- and short-range particulate order. These results are discussed by analogy to the x-ray diffraction of crystals and glasses as is the practical applicability of “photonic glasses” with respect to the more widely studied “photonic crystals.”

Photoluminescent Characterization of Atomic Diffusion in Core-Shell Nanoparticles

Eu3+ doped LaF3 nanoparticles with core/shell morphologies were synthesized and selected spectroscopic properties were measured as a function of heat treatment times and temperatures. More specifically, the relative intensity of photoluminescence spectra, both through direct excitation of the lanthanide as well as phonon sideband spectra were evaluated with increasing amounts of time held at specific temperatures. A one dimensional approximation was used to compute an effective diffusion coefficient for the rare earth dopants in LaF3. Despite the simplicity of the model employed, the calculated diffusion coefficients based on the spectroscopic results are accurate within an order of magnitude in comparison to other fluoride crystals yielding a simplified approach to estimating kinetic and diffusion effects in optical materials.

Transparent silica glasses containing single-walled carbon nanotubes

Organic - Inorganic matrix nano composites have been created using an acid catalyzed, tetraethyl orthosilicate-based sol- gel technique with SWNTs. By utilizing nanotubes functionalized with the dendron methyl 3,5- di(methyltrigycoloxy)benzylic alcohol, ultrasonication blending in the sol phase prior to gelation yields excellent dispersion characteristics of the nanotube phase. Further, glasses could easily be dried by heating to 600 degrees C yielding 80 percent of theoretical density wit little change in the nanotube content. These materials exhibited intrinsic Rayleigh scattering, suggesting near ideal dispersion. Nonlinear optical transmissivity was observed for 1064 and 532 nm light suggesting that the matrix has a strong broad band coupling to the optical field. Such composites allow for a host of applications based on the novel confinement properties of carbon nanotubes in a robust host.

Ultra-broadband amplification through nanotechnology

As demands for bandwidth continue to increase, telecommunication networks would greatly benefit from the development of broader-band amplifiers. The currently erbium doped fiber amplifiers are limited to amplification of approximately 100 nm bandwidth window. One method to increase the bandwidth of the fiber amplifier would be to incorporate multiple rare earths (REs) into a single fiber which exhibit emissions from ~1000-1800 nm. Unfortunately, energy transfer between rare earth ions typically results in quenching all but selected emissions negating this approach to potential ultra-broadband amplification. It would be ideal if one could take the individual spectra of an ion and place that ion into a host with no regard to other lanthanides that also are present in the host. This problem can be solved by using a composite material that utilizes nanoparticles to constrain different REs to individual particles thereby controlling or preventing energy transfer. In order to control energy transfer, RE doped LaF3 nanocrystals were grown in an aqueous solution using a core/shell technique to constrain different rare earth into separate particles or shells within a single particle. Using these techniques, we show that energy transfer can be controlled.