Photoluminescence lifetimes and optical absorption cross sections of Si nanocrystals embedded in SiO2 have been studied as a function of their average size and emission energy. The lifetimes span from 20 μs for the smallest sizes (2.5 nm) to more than 200 μs for the largest ones (7 nm). The passivation of nonradiative interface states by hydrogenation increases the lifetime for a given size. In contrast with porous Si, the cross section per nanocrystal shows a nonmonotonic behavior with emission energy. In fact, although the density of states above the gap increases for larger nanocrystals, this trend is compensated by a stronger reduction of the oscillator strength, providing an overall reduction of the absorption cross section per nanocrystal for increasing size.

This paper investigates the interaction between Si nanoclusters ͑Si-nc͒ and Er in SiO 2 , reports on the optical characterization and modeling of this system, and attempts to clarify its effectiveness as a gain material for optical waveguide amplifiers at 1.54 m. Silicon-rich silicon oxide layers with an Er content of 4 -6 ϫ 10 20 at./ cm 3 were deposited by reactive magnetron sputtering. The films with Si excess of 6 -7 at. %, and postannealed at 900°C showed the best Er 3+ photoluminescence ͑PL͒ intensity and lifetime, and were used for the study. The annealing duration was varied up to 60 min to engineer the size and density of Si-nc and optimize Si-nc and Er coupling. PL investigations under resonant ͑488 nm͒ and nonresonant ͑476 nm͒ pumping show that an Er effective excitation cross section is similar to that of Si-nc ͑ϳ10 −17 -10 −16 cm 2 ͒ at low pumping flux ͑ϳ1016 -10 17 cm −2 s −1 ͒, while it drops at high flux ͑Ͼ10 18 cm −2 s −1 ͒. We found a maximum fraction of excited Er of about 2% of the total Er content. This is far from the 50% needed for optical transparency and achievement of population inversion and gain. Detrimental phenomena that cause depletion of Er inversion, such as cooperative up conversion, excited-stated absorption, and Auger deexcitations are modeled, and their impact in lowering the amount of excitable Er is found to be relatively small. Instead, Auger-type short-range energy transfer from Si-nc to Er is found, with a characteristic interaction length of 0.4 nm. Based on such results, numerical and analytical ͑Er as a quasi-two-level system͒ coupled rate equations have been developed to determine the optimum conditions for Er inversion. The modeling predicts that interaction is quenched for high photon flux and that only a small fraction of Er ͑0.2-2 %͒ is excitable through Si-nc. Hence, the low density of sensitizers ͑Si-nc͒ and the short range of the interaction are the explanation of the low fraction of Er coupled. Efficient ways to improve Er-doped Si-nc thin films for the realization of practical optical amplifiers are also discussed.

Influence of average size and interface passivation on the spectral emission of Si nanocrystals embedded in SiO 2

Si excess, Er content, and processing parameters have been optimized in a series of cosputtered oxide layers for maximizing Er emission and lifetime. The amount of excited Er as a function of the incident photon flux has been quantified for resonant (488nm) and nonresonant (476nm) excitations. Results show that a maximum of 3.5% of Er ions is excitable through the Si nanoclusters (Si-nc). This low value cannot be explained only by cooperative upconversion and/or excited state absorption. A short range (0.5nm) distance dependent interaction model is developed that accounts for this low Er population inversion. The model points to the low density of Si-nc [(3–5)×1017cm−3] as the ultimate limiting step for indirect Er excitation in this system.

The correlation between the structural ͑average size and density͒ and optoelectronic properties ͓band gap and photoluminescence ͑PL͔͒ of Si nanocrystals embedded in SiO 2 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 SiO 2 . With this aim, we have recently developed a successful method for imaging Si nanocrystals in SiO 2 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 N 2 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 P b paramagnetic centers at the Si-SiO 2 nanocrystal-matrix interfaces, which have been measured by electron spin resonance. Consequently, the P b 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 0.26Ϯ0.03 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 SiO 2 is a fundamental transition spatially located at the Si-SiO 2 interface with the assistance of a local Si-O vibration.

Administration of repeated doses of MSCs by subarachnoid route is a well-tolerated procedure that is able to achieve progressive and significant improvement in the quality of life of patients suffering incomplete SCI.

Pump and probe experiments on Er3+ ions coupled to Si nanoclusters have been performed in rib-loaded waveguides to investigate optical amplification at 1.5μm. Rib-loaded waveguides were obtained by photolithographic and reactive ion etching of Er-doped silica layers containing Si nanoclusters grown by reactive sputtering. Insertion losses measurements in the infrared erbium absorption region allowed to gauge an Er3+ absorption cross section of about 5×10−21cm2 at 1534nm. Signal transmission under optical pumping at 1310nm shows confined carrier absorption of the Si nanoclusters. Amplification experiments at 1535nm evidence two pump power regimes: Losses due to confined carrier absorption in the Si nanoclusters at low pump powers and signal enhancement at high pump powers. For strong optical pumping, signal enhancement of about 1.2dB∕cm was obtained.

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