Sebastien Hamel

Light emission from silicon-rich nitride nanostructures

Light-emitting Si-rich silicon nitride (SRN) films were fabricated by plasma enhanced chemical vapor deposition followed by low temperature (500–900°C) annealing. The optical properties of SRN films were studied by micro-Raman and photoluminescence spectroscopy and indicate the presence of small Si clusters characterized by broad near-infrared emission, large absorption/emission Stokes shift, and nanosecond recombination. Our results are supported by first-principles simulations indicating that N atoms bonded to the surface of nanometer Si clusters play a crucial role in the emission mechanism of SRN films. Light emission from SRN systems can provide alternative routes towards the fabrication of optically active Si devices.

Phase separation in hydrogen–helium mixtures at Mbar pressures

The properties of hydrogen–helium mixtures at Mbar pressures and intermediate temperatures (4000 to 10000 K) are calculated with first-principles molecular dynamics simulations. We determine the equation of state as a function of density, temperature, and composition and, using thermodynamic integration, we estimate the Gibbs free energy of mixing, thereby determining the temperature, at a given pressure, when helium becomes insoluble in dense metallic hydrogen. These results are directly relevant to models of the interior structure and evolution of Jovian planets. We find that the temperatures for the demixing of helium and hydrogen are sufficiently high to cross the planetary adiabat of Saturn at pressures ≈5 Mbar; helium is partially miscible throughout a significant portion of the interior of Saturn, and to a lesser extent in Jupiter.

Pulse Shape Discrimination in Impure and Mixed Single-Crystal Organic Scintillators

Neutron/gamma pulse shape discrimination (PSD) utilized for detection of high-energy neutrons with organic scintillators was investigated using a model system of mixed diphenylacetylene-stilbene single crystals of different compositions. The results of the studies, which include experimental tools of crystal growth and characterization combined with computer simulation, showed that the presence of impurities with lower bandgap energies can be a major factor influencing PSD properties of organic materials. Depending on the concentration, an impurity may suppress or increase the rate of excited triplet state interaction leading, respectively, to a complete disappearance or enhancement of PSD, consistent with a percolation threshold. The results are applied to produce novel materials with controlled decay characteristics. Single crystals with a large fraction of delayed light and enhanced PSD have been grown for high energy neutron detection, while crystals with suppressed delayed light were produced for use as low-afterglow scintillators for energetic neutron detection in time-of-flight experiments.

Exchange-only optimized effective potential for molecules from resolution-of-the-identity techniques: Comparison with the local density approximation, with and without asymptotic correction

The optimized effective potential (OEP) is (within a certain linear response approximation) the exact exchange-correlation potential of density-functional theory (DFT). In the program DEMON-DYNARHO, we have implemented the OEP at the exchange-only level without the evaluation of four-center integrals using resolution-of-the-identity techniques. We point out that great care must be taken in treating the asymptotic behavior of the OEP in finite basis set methods. Our results are compared with previous work using OEP-like potentials. Our OEP orbital energies are compared with experimental ionization potentials, Hartree–Fock (HF) orbital energies, and with orbital energies from the local density approximation (LDA) potential, with and without asymptotic correction (AC). We find that OEP orbital energies are a much better approximation to experimental ionization potentials than are HF orbital energies. LDA orbital energies also correlate well with OEP orbital energies, except for a molecule-dependent rigid shi...

Light-Emitting Silicon Nanocrystals and Photonic Structures in Silicon Nitride

In this paper, we review our main results on the optical and electrical properties of light-emitting silicon nanocrystals (Si-ncs) obtained from the thermally induced nucleation in amorphous silicon-rich nitride (SRN) films deposited either by plasma-enhanced chemical vapor deposition (PE-CVD) or magnetron sputtering. In particular, we discuss the Si-ncs microscopic light emission mechanism combining the optical data with the first-principle calculations of the absorption/emission Stokes shifts and recombination lifetimes. In addition, we report on the electrical injection characteristics of simple p-i-n device structures showing efficient bipolar transport and room temperature electroluminescence, and demonstrate efficient energy sensitization of erbium (Er) ions from the Si-ncs embedded in the SRN matrices. We further show that the light-emitting nanocrystals in SRN can be embedded in aperiodic photonic environments, where the localized optical modes can be used to significantly enhance the Si-ncs emission intensity at different emission wavelengths. These results suggest that the Si-ncs embedded in the SRN matrices have a large potential for the fabrication of optically active photonic devices based on the Si technology

Multiphase equation of state for carbon addressing high pressures and temperatures

We present a 5-phase equation of state for elemental carbon which addresses a wide range of density and temperature conditions: 3g/cc 100000K(bothfor ρ between3and12g/cc,withselecthigher-ρ DFTcalculationsas well). The liquid free energy model includes an atom-in-jellium approach to account for the effects of ionization due to temperature and pressure in the plasma state, and an ion-thermal model which includes the approach to the ideal gas limit. The precise manner in which the ideal gas limit is reached is greatly constrained by both the highest-temperature DFT data and the path integral data, forcing us to discard an ion-thermal model we had used previously in favor of a new one. Predictions are made for the principal Hugoniot and the room-temperature isotherm, and comparisons are made to recent experimental results.

Assessment of the quality of orbital energies in resolution-of-the-identity Hartree–Fock calculations using deMon auxiliary basis sets

The Roothaan–Hartree–Fock (HF) method has been implemented in deMon–DynaRho within the resolution-of-the-identity (RI) auxiliary-function approximation. While previous studies have focused primarily upon the effect of the RI approximation on total energies, very little information has been available regarding the effect of the RI approximation on orbital energies, even though orbital energies play a central role in many theories of ionization and excitation. We fill this gap by testing the accuracy of the RI approximation against non-RI-HF calculations using the same basis sets, for the occupied orbital energies and an equal number of unoccupied orbital energies of five small molecules, namely CO, N2, CH2O, C2H4, and pyridine (in total 102 orbitals). These molecules have well-characterized excited states and so are commonly used to test and validate molecular excitation spectra computations. Of the deMon auxiliary basis sets tested, the best results are obtained with the (44) auxiliary basis sets, yieldin...

Analysis of laser shock experiments on precompressed samples using a quartz reference and application to warm dense hydrogen and helium

Megabar (1 Mbar = 100 GPa) laser shocks on precompressed samples allow reaching unprecedented high densities and moderately high ∼103–104 K temperatures. We describe here a complete analysis framework for the velocimetry (VISAR) and pyrometry (SOP) data produced in these experiments. Since the precompression increases the initial density of both the sample of interest and the quartz reference for pressure-density, reflectivity, and temperature measurements, we describe analytical corrections based on available experimental data on warm dense silica and density-functional-theory based molecular dynamics computer simulations. Using our improved analysis framework, we report a re-analysis of previously published data on warm dense hydrogen and helium, compare the newly inferred pressure, density, and temperature data with most advanced equation of state models and provide updated reflectivity values.

Structural and optical properties of liquid CO2 for pressures up to 1 TPa

We report on the use of first-principles molecular dynamics calculations to examine properties of liquid carbon dioxide in the pressure-temperature range of 0-1 TPa and 200-100 000 K. The computed equations of state points are used to predict a series of shock Hugoniots with initial starting conditions that are relevant to existing and ongoing shock-wave experiments. A comparison with published measurements up to 70 GPa shows excellent agreement. We find that the liquid undergoes a gradual phase transition along the Hugoniot and have characterized this transition based on changes in bonding and structural properties as well as the conductivity and reflectivity of the fluid.

Neutron detection with single crystal organic scintillators

Detection of high-energy neutrons in the presence of gamma radiation background utilizes pulse-shape discrimination (PSD) phenomena in organics studied previously only with limited number of materials, mostly liquid scintillators and single crystal stilbene. The current paper presents the results obtained with broader varieties of luminescent organic single crystals. The studies involve experimental tools of crystal growth and material characterization in combination with the advanced computer modeling, with the final goal of better understanding the relevance between the nature of the organic materials and their PSD properties. Special consideration is given to the factors that may diminish or even completely obscure the PSD properties in scintillating crystals. Among such factors are molecular and crystallographic structures that determine exchange coupling and exciton mobility in organic materials and the impurity effect discussed on the examples of trans-stilbene, bibenzyl, 9,10- diphenylanthracene and diphenylacetylene.