Joel Therrien

Observation of a magic discrete family of ultrabright Si nanoparticles

We demonstrate that electrochemically etched, hydrogen capped SinHx clusters with n larger than 20 are obtained within a family of discrete sizes. These sizes are 1.0 (Si29), 1.67 (Si123), 2.15, 2.9, and 3.7 nm in diameter. We characterize the particles via direct electron imaging, excitation and emission optical spectroscopy, and colloidal crystallization. The band gaps and emission bands are measured. The smallest four are ultrabright blue, green, yellow and red luminescent particles. The availability of discrete sizes and distinct emission in the red, green and blue (RGB) range is useful for biomedical tagging, RGB displays, and flash memories.

Oxide and hydrogen capped ultrasmall blue luminescent Si nanoparticles

We dispersed electrochemical etched silicon into a colloid of ultrasmall ultrabright Si nanoparticles. Direct imaging using transmission electron microscopy shows particles of ∼1 nm in diameter, and infrared and electron photospectroscopy show that they are passivated with hydrogen. Under 350 nm excitation, the luminescence is dominated by an extremely strong blue band at 390 nm. We replace hydrogen by a high-quality ultrathin surface oxide cap by self-limiting oxidation in H2O2. Upon capping, the excitation efficiency drops, but only by a factor of 2, to an efficiency still two-fold larger than that of fluorescein. Although of slightly lower brightness, capped Si particles have superior biocompatability, an important property for biosensing applications.

Detection of luminescent single ultrasmall silicon nanoparticles using fluctuation correlation spectroscopy

We dispersed electrochemical etched Si into a colloid of ultrasmall blue luminescent nanoparticles, observable with the naked eye, in room light. We use two-photon near-infrared femtosecond excitation at 780 nm to record the fluctuating time series of the luminescence, and determine the number density, brightness, and size of diffusing fluorescent particles. The luminescence efficiency of particles is high enough such that we are able to detect a single particle, in a focal volume, of 1 pcm3. The measurements yield a particle size of 1 nm, consistent with direct imaging by transmission electron microscopy. They also yield an excitation efficiency under two-photon excitation two to threefold larger than that of fluorescein. Detection of single particles paves the way for their use as labels in biosensing applications.

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.

Effect of surface reconstruction on the structural prototypes of ultrasmall ultrabright Si29 nanoparticles

We propose, using density functional, configuration interaction, and quantum Monte Carlo calculations, structural prototypes of ultrasmall ultrabright particles prepared by dispersion from bulk. We constructed near spherical structures (Td point group symmetry) that contain 29 Si atoms, five of which constitute a tetrahedral core and the remaining 24 constitute a hydrogen terminated reconstructed Si surface. The surface is a highly wrinkled or puckered system of hexagons and pentagons (as in a filled fullerene). We calculated, for several surface reconstruction models, the coordinates of atoms, the absorption spectrum, the absorption edge, polarizability, and the electron diffraction pattern. The Si29H24 (six reconstructed surface dimers) gives a size of 0.9 nm, an absorption spectrum and bandgap (3.5±0.3 eV), in fair agreement with measurement. The structure yields a polarizability of 830 a.u. with an effective “dielectric” constant of ∼6.0. The calculated electron diffraction of single particles shows r...

Observation of laser oscillation in aggregates of ultrasmall silicon nanoparticles

We report laser oscillation at ∼610 nm in aggregates of ultrasmall elemental Si nanoparticles. The particles are ultrabright red emitting, dispersed from bulk Si by electrochemistry. The aggregates are excited by radiation at 550–570 nm from a mercury lamp. Intense directed Gaussian beams, with a threshold, manifest the emission. We observe line narrowing, and speckle patterns, indicating spatial coherence. This microlasing constitutes an important step towards the realization of a laser on a chip, hence optoelectronics integration and optical interconnects.

Highly nonlinear photoluminescence threshold in porous silicon

Porous silicon is excited using near-infrared femtosecond pulsed and continuous wave radiation at an average intensity of ∼106 W/cm2 (8×1010 W/cm2 peak intensity in pulsed mode). Our results demonstrate the presence of micron-size regions for which the intensity of the photoluminescence has a highly nonlinear threshold, rising by several orders of magnitude near this incident intensity for both the pulsed and continuous wave cases. These results are discussed in terms of stimulated emission from quantum confinement engineered intrinsic Si–Si radiative traps in ultrasmall nanocrystallites, populated following two-photon absorption.

Thin film silicon nanoparticle UV photodetector

We constructed ultraviolet (UV) photodetectors by room-temperature deposition of Si nanoparticle films on Si p-type substrates. Silicon nanoparticles of 1-nm diameter are dispersed from Si wafers using electrochemical etching. The current-voltage characteristics indicate a photoconductor in series with a diode-like junction with a large enhancement in the forward current under UV illumination. With increasing wavelength, the response drops rapidly, dropping to a few percent at 560 nm. These results point to a sensitive UV detector with good visible blindness where the particle films effectively constitutes a wide-bandgap material.

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.

UV photodetectors with thin-film Si nanoparticle active medium

We constructed ultraviolet (UV) photodetectors using thin films of silicon nanoparticles as active media. The Si nanoparticle films are electrodeposited at room temperature on Si p-type substrates. Uniform silicon nanoparticles of 1-nm diameter are dispersed from Si wafers using electrochemical etching. The nanoparticles are ultrabright under UV excitation, with nanosecond luminescence time characteristics. Current-voltage (I--V) characteristics indicate a photoconductor in series with a diode-like junction with a large enhancement in the forward current under UV illumination. Our results point to a sensitive UV detector with good visible blindness where the particle films effectively constitutes a wide-bandgap material.