Influence of average size and interface passivation on the spectral emission of Si nanocrystals embedded in SiO2

The correlation between the structural (average size and density) and optoelectronic properties [band gap and photoluminescence (PL)] of Si nanocrystals embedded in SiO2 is among the essential factors in understanding their emission mechanism. This correlation has been difficult to establish in the past due to the lack of reliable methods for measuring the size distribution of nanocrystals from electron microscopy, mainly because of the insufficient contrast between Si and SiO2. With this aim, we have recently developed a successful method for imaging Si nanocrystals in SiO2 matrices. This is done by using high-resolution electron microscopy in conjunction with conventional electron microscopy in dark field conditions. Then, by varying the time of annealing in a large time scale we have been able to track the nucleation, pure growth, and ripening stages of the nanocrystal population. The nucleation and pure growth stages are almost completed after a few minutes of annealing time at 1100°C in N2 and afterward the ensemble undergoes an asymptotic ripening process. In contrast, the PL intensity steadily increases and reaches saturation after 3-4 h of annealing at 1100°C. Forming gas postannealing considerably enhances the PL intensity but only for samples annealed previously in less time than that needed for PL saturation. The effects of forming gas are reversible and do not modify the spectral shape of the PL emission. The PL intensity shows at all times an inverse correlation with the amount of Pb paramagnetic centers at the Si-SiO2 nanocrystal-matrix interfaces, which have been measured by electron spin resonance. Consequently, the Pb centers or other centers associated with them are interfacial nonradiative channels for recombination and the emission yield largely depends on the interface passivation. We have correlated as well the average size of the nanocrystals with their optical band gap and PL emission energy. The band gap and emission energy shift to the blue as the nanocrystal size shrinks, in agreement with models based on quantum confinement. As a main result, we have found that the Stokes shift is independent of the average size of nanocrystals and has a constant value of 0.26±0.03 eV, which is almost twice the energy of the Si¿O vibration. This finding suggests that among the possible channels for radiative recombination, the dominant one for Si nanocrystals embedded in SiO2 is a fundamental transition spatially located at the Si¿SiO2 interface with the assistance of a local Si-O vibration.

Reliure de : I Discorsi di M. Pietro Andrea Matthioli,... nelli sei libri di Pedacio Dioscoride,... della materia medicinale, hora di nuovo dal suo istesso autore ricorretti et... aumentati... con due tavole copiosissime... - Del Modo di distillare le acque da tutte le piante, et come vi si possino conservare i loro veri odori et sapori

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Spin-orbit effects in GaAs quantum wells: Interplay between Rashba, Dresselhaus, and Zeeman interactions

The interplay between Rashba, Dresselhaus, and Zeeman interactions in a quantum well submitted to an external magnetic field is studied by means of an accurate analytical solution of the Hamiltonian, including electron-electron interactions in a sum-rule approach. This solution allows us to discuss the influence of the spin-orbit coupling on some relevant quantities that have been measured in inelastic light scattering and electron-spin resonance experiments on quantum wells. In particular, we have evaluated the spin-orbit contribution to the spin splitting of the Landau levels and to the splitting of charge- and spin-density excitations. We also discuss how the spin-orbit effects change if the applied magnetic field is tilted with respect to the direction perpendicular to the quantum well.

Spin-orbit effects in GaAs quantum wells: Interplay between Rashba, Dresselhaus, and Zeeman interactions

The interplay between Rashba, Dresselhaus, and Zeeman interactions in a quantum well submitted to an external magnetic field is studied by means of an accurate analytical solution of the Hamiltonian, including electron-electron interactions in a sum-rule approach. This solution allows us to discuss the influence of the spin-orbit coupling on some relevant quantities that have been measured in inelastic light scattering and electron-spin resonance experiments on quantum wells. In particular, we have evaluated the spin-orbit contribution to the spin splitting of the Landau levels and to the splitting of charge- and spin-density excitations. We also discuss how the spin-orbit effects change if the applied magnetic field is tilted with respect to the direction perpendicular to the quantum well.

Heat capacity measurements on the equiatomic compounds in Ni-X (X = Al, In, Si, Ge and Bi) and M-Sb (with M = Ni, Co and Fe) systems

Molar heat capacities of the binary compounds NiAl, NiIn, NiSi, NiGe, NiBi, NiSb, CoSb and FeSb were determined every 10 K by differential scanning calorimetry in the temperature range 310-1080 K. The experimental results have been fitted versus temperature according to C-p = a + b . T + c . T-2 + d . T-2. Results are given, discussed and compared to estimations found in the literature. Two compounds, NiBi and FeSb, are subject to transformations between 460 and 500 K. (C) 1999 Elsevier Science Ltd. All rights reserved.

Ellipsometric study of a-Si:H thin films deposited by square wave modulated rf glow discharge

Thin films of hydrogenated amorphous silicon (a‐Si:H), deposited by square wave modulated (SQWM) rf silane discharges, have been studied through spectroscopic and real time phase modulated ellipsometry. The SQMW films obtained at low mean rf power density (19 mW/cm2) have shown smaller surface roughness than those obtained in standard continuous wave (cw) rf discharges. At higher rf powers (≥56 mW/cm2), different behaviors depending on the modulating frequency have been observed. On the one hand, at low modulating frequencies (<40 Hz), the SQWM films have shown a significant increase of porosity and surface roughness as compared to cw samples. On the other, at higher modulating frequencies, the material density and roughness have been found to be similar in SQWM and cw films. Furthermore, the deposition rate of the films show more pronounced increases with the modulating frequency as the rf power is increased. Experimental results are discussed in terms of plasma negative charged species which can be relatively abundant in high rf power discharges and cause significant effects on the deposited layers through polymers, clusters, and powder formation.

On the determination of the interface density of states in a-Si:H/a-SiC:H multilayers

This paper deals with the determination of the interface density of states in amorphous silicon-based multilayers. Photothermal deflection spectroscopy is used to characterize two series of aSi:H/aSi1-xCx:H multilayers, and a new approach in the treatment of experimental dada is used in order to obtain accurate results. From this approach, an upper limit of 10^10 cm-2 is determined for the interface density of states.

Polymorphous Si thin films from radio frequency plasmas of SiH4 diluted in Ar: A study by transmission electron microscopy and Raman spectroscopy

In this study, we present a detailed structural characterization by means of transmission electron microscopy and Raman spectroscopy of polymorphous silicon (pm-Si:H) thin films deposited using radio-frequency dust-forming plasmas of SiH4 diluted in Ar. Square-wave modulation of the plasma and gas temperature was varied to obtain films with different nanostructures. Transmission electron microscopy and electron diffraction have shown the presence of Si crystallites of around 2 nm in the pm-Si:H films, which are related to the nanoparticles formed in the plasma gas phase coming from their different growth stages, named particle nucleation and coagulation. Raman scattering has proved the role of the film nanostructure in the crystallization process induced ¿in situ¿ by laser heating.

Atomic structure of the nanocrystalline Si particles appearing in nanostructured Si thin films produced in low-temperature radiofrequency plasmas

Nanostructured Si thin films, also referred as polymorphous, were grown by plasma-enhanced chemical vapor deposition. The term "polymorphous" is used to define silicon material that consists of a two-phase mixture of amorphous and ordered Si. The plasma conditions were set to obtain Si thin films from the simultaneous deposition of radical and ordered nanoparticles. Here, a careful analysis by electron transmission microscopy and electron diffraction is reported with the aim to clarify the specific atomic structure of the nanocrystalline particles embedded in the films. Whatever the plasma conditions, the electron diffraction images always revealed the existence of a well-defined crystalline structure different from the diamondlike structure of Si. The formation of nanocrystallinelike films at low temperature is discussed. A Si face-cubic-centered structure is demonstrated here in nanocrystalline particles produced in low-pressure silane plasma at room temperature.

Calorimetry of hydrogen desorption from a-Si nanoparticles

The process of hydrogen desorption from amorphous silicon (a-Si) nanoparticles grown by plasma-enhanced chemical vapor deposition (PECVD) has been analyzed by differential scanning calorimetry (DSC), mass spectrometry, and infrared spectroscopy, with the aim of quantifying the energy exchanged. Two exothermic peaks centered at 330 and 410 C have been detected with energies per H atom of about 50 meV. This value has been compared with the results of theoretical calculations and is found to agree with the dissociation energy of Si-H groups of about 3.25 eV per H atom, provided that the formation energy per dangling bond in a-Si is about 1.15 eV. It is shown that this result is valid for a-Si:H films, too.