Eric J. Henderson

Solution phase synthesis of carbon quantum dots as sensitizers for nanocrystalline TiO2 solar cells

Carbon quantum dots (CQDs) have recently emerged as viable alternatives to traditional semiconductor quantum dots because of their facile and low cost synthesis, long term colloidal stability, and low environmental and biological toxicity. The compatible surface chemistry, good solubility in polar solvents and extensive optical absorption throughout the visible and near-infrared wavelength regions render CQDs as potentially useful sensitizers for photovoltaic applications. Presented herein is a new strategy for the solution phase synthesis of water-soluble, colloidally stable CQDs and a preliminary exploration of their utilization as sensitizers in nanocrystalline TiO2 based solar cells. Under AM 1.5 illumination, the Voc and FF values reach 380 mV and 64% respectively, achieving a power conversion efficiency of 0.13%.

Visible Colloidal Nanocrystal Silicon Light-Emitting Diode

We herein demonstrate visible electroluminescence from colloidal silicon in the form of a hybrid silicon quantum dot-organic light emitting diode. The silicon quantum dot emission arises from quantum confinement, and thus nanocrystal size tunable visible electroluminescence from our devices is highlighted. An external quantum efficiency of 0.7% was obtained at a drive voltage where device electroluminescence is dominated by silicon quantum dot emission. The characteristics of our devices depend strongly on the organic transport layers employed as well as on the choice of solvent from which the Si quantum dots are cast.

Preparation of Monodisperse Silicon Nanocrystals Using Density Gradient Ultracentrifugation

We report the preparation of monodisperse silicon nanocrystals (ncSi) by size-separation of polydisperse alkyl-capped ncSi using organic density gradient ultracentrifugation. The ncSi were synthesized by thermal processing of trichlorosilane-derived sol-gel glasses followed by HF etching and surface passivation with alkyl chains and were subsequently fractionated by size using a self-generating density gradient of 40 wt % 2,4,6-tribromotoluene in chlorobenzene. The isolated monodisperse fractions were characterized by photoluminescence spectroscopy and high-angle annular dark-field scanning transmission electron microscopy and determined to have polydispersity index values between 1.04 and 1.06. The ability to isolate monodisperse ncSi will allow for the quantification of the size-dependent structural, optical, electrical, and biological properties of silicon, which will undoubtedly prove useful for tailoring property-specific optoelectronic and biomedical devices.

Synthesis and Photoluminescent Properties of Size-Controlled Germanium Nanocrystals from Phenyl Trichlorogermane-Derived Polymers

We report the preparation of luminescent oxide-embedded germanium nanocrystals (Ge-NC/GeO2) by the reductive thermal processing of polymers derived from phenyl trichlorogermane (PTG, C6H5GeCl3). Sol-gel processing of PTG yields air-stable polymers with a Ge:O ratio of 1:1.5, (C6H5GeO1.5)n, that thermally decompose to yield a germanium rich oxide (GRO) network. Thermal disproportionation of the GRO results in nucleation and initial growth of oxide-embedded Ge-NC, and subsequent reaction of the GeO2 matrix with the reducing atmosphere results in additional nanocrystal growth. This synthetic method affords quantitative yields of composite powders in large quantities and allows for Ge-NC size control through variations of the peak thermal processing temperature and reaction time. Freestanding germanium nanocrystals (FS-Ge-NC) are readily liberated from Ge-NC/GeO2 composite powders by straightfoward dissolution of the oxide matrix in warm water. Composites and FS-Ge-NC were characterized using thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDX), and photoluminescence (PL) spectroscopy.

Colloidally stable silicon nanocrystals with near-infrared photoluminescence for biological fluorescence imaging.

Luminescent silicon nanocrystals (ncSi) are showing great promise as photoluminescent tags for biological fluorescence imaging, with size-dependent emission that can be tuned into the near-infrared biological window and reported lack of toxicity. Here, colloidally stable ncSi with NIR photoluminescence are synthesized from (HSiO1.5)n sol-gel glasses and are used in biological fluorescence imaging. Modifications to the thermal processing conditions of (HSiO1.5)n sol-gel glasses, the development of new ncSi oxide liberation chemistry, and an appropriate alkyl surface passivation scheme lead to the formation of colloidally stable ncSi with photoluminescence centered at 955 nm. Water solubility and biocompatibility are achieved through encapsulation of the hydrophobic alkyl-capped ncSi within PEG-terminated solid lipid nanoparticles. Their applicability to biological imaging is demonstrated with the in-vitro fluorescence labelling of human breast tumor cells.

Colloidally Stable Germanium Nanocrystals for Photonic Applications

We report the development of a straightforward synthesis for colloidally stable germanium nanocrystals for use as a solution-processable precursor for the bottom-up fabrication of functional thin films. SiO(2)-embedded germanium nanocrystals are produced by the reductive thermal processing of sol-gel glasses derived from mixtures of tetraethoxyorthogermanate (TEOG) and tetraethoxyorthosilicate (TEOS), and free-standing germanium nanocrystals are liberated from the encapsulating silicon dioxide through sequential chemical etching. The applicability of these germanium nanocrystals as a solution-processable thin film precursor is demonstrated by the fabrication of high refractive index thin films.

From phenylsiloxane polymer composition to size-controlled silicon carbide nanocrystals.

Silicon carbide (SiC) has become a very important material for many high-performance applications as a result of its exceptional material properties. The emergence of size-dependent properties in SiC nanocrystals (SiC-NCs), together with the increased surface area intrinsic to nanocrystals, has led to a variety of new possible applications, including optoelectronics and hybrid materials. Here we report the straightforward preparation of size-controlled oxide-embedded and freestanding SiC-NCs from the reductive thermal processing of compositionally controlled phenylsiloxane polymers. Compositional tuning of the polymers is achieved by varying the relative amounts of phenyl trichlorosilane (C(6)H(5)SiCl(3)) and silicon tetrachloride (SiCl(4)) during hydrolysis and cocondensation. Thermal processing of the resulting compositionally controlled condensation copolymers yields oxide-embedded SiC-NCs whose average diameter is dependent on the relative C(6)H(5)SiCl(3) concentration in the initial precursor mixture. A liberation procedure for preparing size-controlled freestanding SiC-NCs that involves oxidation of matrix carbon and subsequent chemical etching of the matrix is also presented.

Assembling Photoluminescent Silicon Nanocrystals into Periodic Mesoporous Organosilica

A contemporary question in the intensely active field of periodic mesoporous organosilica (PMO) materials is how large a silsesquioxane precursor can be self-assembled under template direction into the pore walls of an ordered mesostructure. An answer to this question is beginning to emerge with the ability to synthesize dendrimer, buckyball, and polyhedral oligomeric silsesquioxane PMOs. In this paper, we further expand the library of large-scale silsesquioxane precursors by demonstrating that photoluminescent nanocrystalline silicon that has been surface-capped with oligo(triethoxysilylethylene), denoted as ncSi:(CH(2)CH(2)Si(OEt)(3))(n)H, can be self-assembled into a photoluminescent nanocrystalline silicon periodic mesoporous organosilica (ncSi-PMO). A comprehensive multianalytical characterization of the structural and optical properties of ncSi-PMO demonstrates that the material gainfully combines the photoluminescent properties of nanocrystalline silicon with the porous structure of the PMO. This integration of two functional components makes ncSi-PMO a promising multifunctional material for optoelectronic and biomedical applications.

Silicon Nanocrystal OLEDs: Effect of Organic Capping Group on Performance

The synthesis of highly luminescent, colloidally-stable and organically-capped silicon nanocrystals (ncSi) and their incorporation into a visible wavelength organic light-emitting diode (OLED) is reported. By substituting decyl chains with aromatic allylbenzene capping ligands and size-selecting visible emitting ncSi, superior packing density, enhanced charge transport, and an improved photoluminescence absolute quantum yield of the ncSi is obtained in the active layer of an OLED.

Spatially Confined Redox Chemistry in Periodic Mesoporous Hydridosilica–Nanosilver Grown in Reducing Nanopores

Periodic mesoporous hydridosilica, PMHS, is shown for the first time to function as both a host and a mild reducing agent toward noble metal ions. In this archetypical study, PMHS microspheres react with aqueous Ag(I) solutions to form Ag(0) nanoparticles housed in different pore locations of the mesostructure. The dominant reductive nucleation and growth process involves SiH groups located within the pore walls and yields molecular scale Ag(0) nanoclusters trapped and stabilized in the pore walls of the PMHS microspheres that emit orange-red photoluminescence. Lesser processes initiated with pore surface SiH groups produce some larger spherical and worm-shaped Ag(0) nanoparticles within the pore voids and on the outer surfaces of the PMHS microspheres. The intrinsic reducing power demonstrated in this work for the pore walls of PMHS speaks well for a new genre of chemistry that benefits from the mesoscopic confinement of Si-H groups.