Browsing by Subject "Silicon nanocrystals"
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Item First principles calculations of Raman spectra for nanostructures and improved high order forces(2015-12) Bobbitt, Nathaniel Scott; Chelikowsky, James R.; Demkov, Alexander A; Ekerdt, John G; Hwang, Gyeong S; Korgel, Brian AAdvances in computing technology coupled with theoretical developments on the electronic structure problem have laid the foundation for the rapidly growing field of computational materials science. Modern supercomputers are able to perform ab initio calculations of realistic systems containing thousands of atoms. This is an important step forward in the maturation of the field because computational insight can be used to make predictions about or predict experimental data. This dissertation aims to address contemporary theory and practice of solving the electronic structure problem for a variety of nanoscale systems, most of which are of interest for energy application such as photovoltaics or Li-ion batteries. Our calculations are performed within density functional theory using real-space pseudopotentials. In the first part, we examine nanocrystals. We calculate size-dependent properties for ZnO nanocrystals with Al and Ga dopants. Next, we calculate Raman spectra for Si nanocrystals with Li impurities and Si-Ge core-shell structures, which gives us insight into the structure of these nanocrystals. In the second portion, we examine in depth the calculation of interatomic forces within density functional theory and propose a new integration scheme which we demonstrate calculates more accurate bond lengths and vibrational frequencies and improves the stability of molecular dynamics simulations.Item Influence of surface passivation on the photoluminescence from silicon nanocrystals(2010-08) Salivati, Navneethakrishnan; Ekerdt, John G.; Downer, Michael C.; Mullins, C. B.; Korgel, Brian A.; Hwang, Gyeong S.Although silicon (Si) nanostructures exhibit size dependent light emission, which can be attributed to quantum confinement, the role of surface passivation is not yet fully understood. This understanding is central to the development of nanocrystal-based detectors. This study investigated the growth, surface chemistry, passivation with deuterium (D2), ammonia (ND3) and diborane (B2D6) and the resulting optical properties of Si nanostructures. Si nanocrystals less than 6 nm in diameter are grown on SiO2 surfaces in an ultra high vacuum chamber using hot-wire chemical vapor deposition and the as grown surfaces are exposed to atomic deuterium. Temperature programmed desorption (TPD) spectra show that that the nanocrystals surfaces are covered by a mix of monodeuteride, dideuteride and trideuteride species. The manner of filling of the deuteride states on nanocrystals differs from that for extended surfaces as the formation of the dideuteride and trideuteride species is facilitated by the curvature of the nanocrystal. No photoluminescence (PL) is observed from the as grown unpassivated nanocrystals. As the deuterium dose is increased, the PL intensity also begins to increase. This can be associated with increasing amounts of mono-, di- and trideuteride species on the nanocrystal surface, which results in better passivation of the dangling bonds and relaxing of the reconstructed surface. At high deuterium doses, the surface structure breaks down and amorphization of the top layer of the nanocrystal takes place. Amorphization reduces the PL intensity. Finally, as the nanocrystal size is varied, the PL peak shifts, which is characteristic of quantum confinement. The dangling bonds and the reconstructed bonds at the NC surface are also passivated and transformed with D and NDx by using deuterated ammonia (ND3), which is predissociated over a hot tungsten filament prior to adsorption. At low hot wire ND3 doses PL emission is observed at 1000 nm corresponding to reconstructed surface bonds capped by predominantly monodeuteride and Si-ND2 species. As the hot wire ND3 dose is increased, di- and trideuteride species form and intense PL is observed around 800 nm that does not shift with NC size and is associated with defect levels resulting from NDx insertion into the strained Si-Si bonds forming Si2=ND. The PL intensity at 800 nm increases as the ND3 dose is increased and the intensity increase is correlated to increasing concentrations of deuterides. At extremely high ND3 doses PL intensity decreases due to amorphization of the NC surface. In separate experiments, Si NCs were subjected to dissociative (thermal) exposures of ammonia followed by exposures to atomic deuterium. These NCs exhibited size dependent PL and this can be attributed to the prevention of the formation of Si2=ND species. Finally, deuterium-passivated Si NCs are exposed to BDx radicals formed by dissociating deuterated diborane (B2D6) over a hot tungsten filament and photoluminescence quenching is observed. Temperature programmed desorption spectra reveal the presence of low temperature peaks, which can be attributed to deuterium desorption from surface Si atoms bonded to subsurface boron atoms. The subsurface boron likely enhances nonradiative Auger recombination.Item Optical spectroscopy study of silicon nanocrystals(2012-08) Wei, Junwei; Downer, Michael Coffin; Sitz, Greg O.; Li, Xiaoqin; Demkov, Alex; Ekerdt, John G.Silicon nanocrystals (NCs), especially Si NCs embedded in SiO₂, have been studied intensely for decades for their potential application in silicon photonics, especially as efficient room temperature light emitters. Despite progress in fabricating photonic devices from Si NCs, the origin of the efficient photoluminescence (PL), the electronic and microscopic structure of the nanocrystals, and the structure of the elusive NC/SiO₂ interfaces for the oxide-embedded nanocrystals, remain controversial. Optical spectroscopy provides a powerful noninvasive tool for probing the structure of the Si NCs, including the active buried NC/SiO₂ interfaces of embedded particles. In this thesis work, oxide-embedded and free-standing alkyl-passivated silicon nanocrystals, prepared by different techniques, have been studied by linear and nonlinear optical spectroscopies. Cross-polarized 2-beam second-harmonic and sum-frequency generation (XP2-SHG/SFG) has been applied spectroscopically to study oxide embedded Si NCs of different sizes (3 to 5 nm diameter) and interface chemistries. The SHG/SFG spectra of silicon nanocrystals (Si NCs) prepared by implanting Si ions uniformly into silica substrates, then annealing, are compared and contrasted to their spectroscopic ellipsometric (SE) and photoluminescence excitation (PLE) spectra. Three resonances--two close in energy to E₁ (3.4 eV) and E2 (4.27 eV) critical-point resonances of crystalline silicon (c-Si), and a broad resonance intermediate in energy between E₁ and E₂--are observed in all three types of spectra. These features are observed in conjunction with a sharp 520 cm⁻¹ Raman peak characteristic of c-Si and an a-Si tail in the Raman spectra. The appearance of bulk-like CP resonances in the parallel PLE, SE and SHG/SFG spectra from Si NCs suggests the basic electronic structure of the bulk c-Si is preserved in nano-particles as small as 3 nm in diameter, albeit with significant size-dependent modification. At the same time, the prominence of a non-bulk-like resonance intermediate in energy between E₁ and E₂ CPs in all three types of spectra demonstrates the important contribution of nano-interfaces to the electronic structure.We also applied Raman spectroscopy to study oxide-embedded and oxide-free alkyl-passivated Si NCs with diameters ranging from 3 nm to greater than 10 nm synthesized by thermal decomposition of hydrogen silsesquioxane (HSQ). While oxide matrix complicates the size-dependence of the Raman peak shift for oxide-embedded nanocrystals, the Raman peak of the free-standing alkyl-passivated Si NCs shifts monotonically with NC size.