Efficient energy transfer from Si clusters to Er3+ in complex silicate glasses

We present an extensive study of the structural and optical emission properties in aluminum silicates and soda-lime silicates codoped with Si nanoclusters (Si-nc) and Er. Si excess of 5 and 15¿at.¿% and Er concentrations ranging from 2×1019 up to 6×1020¿cm¿3 were introduced by ion implantation. Thermal treatments at different temperatures were carried out before and after Er implantation. Structural characterization of the resulting structures was performed to obtain the layer composition and the size distribution of Si clusters. A comprehensive study has been carried out of the light emission as a function of the matrix characteristics, Si and Er contents, excitation wavelength, and power. Er emission at 1540¿nm has been detected in all coimplanted glasses, with similar intensities. We estimated lifetimes ranging from 2.5¿to¿12¿ms (depending on the Er dose and Si excess) and an effective excitation cross section of about 1×10¿17¿cm2 at low fluxes that decreases at high pump power. By quantifying the amount of Er ions excited through Si-nc we find a fraction of 10% of the total Er concentration. Upconversion coefficients of about 3×10¿18¿cm¿3¿s¿1 have been found for soda-lime glasses and one order of magnitude lower in aluminum silicates.

Linear and nonlinear optical properties of Si nanocrystals in SiO2 deposited by plasma-enhanced chemical-vapor deposition

Linear and nonlinear optical properties of silicon suboxide SiOx films deposited by plasma-enhanced chemical-vapor deposition have been studied for different Si excesses up to 24¿at.¿%. The layers have been fully characterized with respect to their atomic composition and the structure of the Si precipitates. Linear refractive index and extinction coefficient have been determined in the whole visible range, enabling to estimate the optical bandgap as a function of the Si nanocrystal size. Nonlinear optical properties have been evaluated by the z-scan technique for two different excitations: at 0.80¿eV in the nanosecond regime and at 1.50¿eV in the femtosecond regime. Under nanosecond excitation conditions, the nonlinear process is ruled by thermal effects, showing large values of both nonlinear refractive index (n2 ~ ¿10¿8¿cm2/W) and nonlinear absorption coefficient (ß ~ 10¿6¿cm/W). Under femtosecond excitation conditions, a smaller nonlinear refractive index is found (n2 ~ 10¿12¿cm2/W), typical of nonlinearities arising from electronic response. The contribution per nanocrystal to the electronic third-order nonlinear susceptibility increases as the size of the Si nanoparticles is reduced, due to the appearance of electronic transitions between discrete levels induced by quantum confinement.

Influence of the (111) twinning on the formation of diamond cubic/diamond hexagonal heterostructures in Cu-catalyzed Si nanowires

The occurrence of heterostructures of cubic silicon/hexagonal silicon as disks defined along the nanowire (111) growth direction is reviewed in detail for Si nanowires obtained using Cu as catalyst. Detailed measurements on the structural properties of both semiconductor phases and their interface are presented. We observe that during growth, lamellar twinning on the cubic phase along the (111) direction is generated. Consecutive presence of twins along the (111) growth direction was found to be correlated with the origin of the local formation of the hexagonal Si segments along the nanowires, which define quantum wells of hexagonal Si diamond. Finally, we evaluate and comment on the consequences of the twins and wurtzite in the final electronic properties of the wires with the help of the predicted energy band diagram.

Modifications in the Si valence band after ion-beam-induced oxidation

The changes undergone by the Si surface after oxygen bombardment have special interest for acquiring a good understanding of the Si+-ion emission during secondary ion mass spectrometry (SIMS) analysis. For this reason a detailed investigation on the stoichiometry of the builtup surface oxides has been carried out using in situ x-ray photoemission spectroscopy (XPS). The XPS analysis of the Si 2p core level indicates a strong presence of suboxide chemical states when bombarding at angles of incidence larger than 30°. In this work a special emphasis on the analysis and interpretation of the valence band region was made. Since the surface stoichiometry or degree of oxidation varies with the angle of incidence, the respective valence band structures also differ. A comparison with experimentally measured and theoretically derived Si valence band and SiO2 valence band suggests that the new valence bands are formed by a combination of these two. This arises from the fact that Si¿Si bonds are present on the Si¿suboxide molecules, and therefore the corresponding 3p-3p Si-like subband, which extends towards the Si Fermi level, forms the top of the respective new valence bands. Small variations in intensity and energy position for this subband have drastic implications on the intensity of the Si+-ion emission during sputtering in SIMS measurements. A model combining chemically enhanced emission and resonant tunneling effects is suggested for the variations observed in ion emission during O+2 bombardment for Si targets.

Sintesis por implantacion ionica de nanocristales semiconductores para dispositivos en tecnologia de Si

En este artículo se estudia la síntesis de nanocristales semiconductores elementales y compuestos elaborados por implantación iónica en SiO2. En el caso de los nanocristales de Si, se ha desarrollado un estudio sistemático que correlaciona las características de los precipitados y sus propiedades de luminiscencia. Nanopartículas de Ge, que presentan menor emisión pero mayor contraste en Microscopía Electrónica de Transmisión, han sido fabricadas para desarrollar un nuevo método de medida de la densidad de nanocristales en matrices amorfas. Por otro lado, nanopartículas de ZnS dopadas con Mn han sido elaboradas por primera vez con esta técnica, observando la emisión de un pico de luminescencia característico de una transición intra-Mn. Finalmente, se presentan los primeros resultados ópticos de capas coimplantadas con Si+ y C+, que muestran la presencia de tres picos intensos de luminescencia en las regiones roja, verde y azul del espectro visible, que ha sido relacionada con la presencia de diferentes tipos de nanopartículas. Cabe destacar que la emisión simultánea de los tres picos ha permitido la observación de una intensa emisión de luz blanca.

Polarization strategies to improve the emission of a Si-based light source emitting at 1.55 um

We present a electroluminescence (EL) study of the Si-rich silicon oxide (SRSO) LEDs with and without Er3+ ions under different polarization schemes: direct current (DC) and pulsed voltage (PV). The power efficiency of the devices and their main optical limitations are presented. We show that under PV polarization scheme, the devices achieve one order of magnitude superior performance in comparison with DC. Time-resolved measurements have shown that this enhancement is met only for active layers in which annealing temperature is high enough (>1000 ◦C) for silicon nanocrystal (Si-nc) formation. Modeling of the system with rate equations has been done and excitation cross-sections for both Si-nc and Er3+ ions have been extracted.

Enhancement of the photoelectrochemical properties of Cl-doped ZnO nanowires by tuning their coaxial doping profile

Arrays of vertically aligned ZnO:Cl/ZnO core-shell nanowires were used to demonstrate that the control of the coaxial doping profile in homojunction nanostructures can improve their surface charge carrier transfer while conserving potentially excellent transport properties. It is experimentally shown that the presence of a ZnO shell enhances the photoelectrochemical properties of ZnO:Cl nanowires up to a factor 5. Likewise, the ZnO shell promotes the visible photoluminescence band in highly conducting ZnO:Cl nanowires. These lines of evidence are associated with the increase of the nanowires" surface depletion layer

Er-Coupled Si Nanocluster Waveguide

Rib-loaded waveguides containing Er3+-coupled Si nanoclusters (Si-nc) have been produced to observe optical gain at 1535 nm. The presence ofSi-nc strongly improves the efficiency ofEr 3+ excitation but may introduce optical loss mechanisms, such as Mie scattering and confined carrier absorption. Losses strongly affect the possibility of obtaining positive optical gain. Si-nc-related losses have been minimized to 1 dB/cm by lowering the annealing time ofthe Er3+-doped silicon-rich oxide deposited by reactive magnetron cosputtering. Photoluminescence (PL) and lifetime measurements show that all Er3+ ions are optically active while those that can be excited at high pump rates via Si-nc are only a small percentage. Er3+ absorption cross section is found comparable to that ofEr 3+ in SiO 2.However, dependence on the effective refractive index has been found. In pump-probe measurements, it is shown how the detrimental role ofconfined carrier absorption can be attenuated by reducing the annealing time. A maximum signal enhancement ofabout 1.34 at 1535 nm was measured.

Model for the emission of Si+ ions during oxygen bombardment of Si(100) surfaces

The variation in the emission of Si+ ions from ion-beam-induced oxidized silicon surfaces has been studied. The stoichiometry and the electronic structure of the altered layer has been characterized using x-ray photoelectron spectroscopy (XPS). The XPS analysis of the Si 2p core level indicates the strong presence of suboxide chemical states when bombarding at angles of incidence larger than 30 °. Since the surface stoichiometry or degree of oxidation varies with the angle of incidence, the corresponding valence-band structures also differ among each other. A comparison between experimental measurements and theoretically calculated Si and SiO2 valence bands indicates that the valence bands for the altered layers are formed by a combination of those two. Since Si-Si bonds are present in the suboxide molecules, the top of the respective new valence bands are formed by the corresponding 3p-3p Si-like subbands, which extend up to the Si Fermi level. The changes in stoichiometry and electronic structure have been correlated with the emission of Si+ ions from these surfaces. From the results a general model for the Si+ ion emission is proposed combining the resonant tunneling and local-bond-breaking models.

Si nanocrystal-based LEDs fabricated by ionimplantation and plasma-enhanced chemical vapourdeposition

Dept. Electrònica

Effects of Nb doping on the TiO2 anatase-to-rutile phase transition

We study the influence of Nb doping on the TiO2 anatase-to-rutile phase transition, using combined transmission electron microscopy, Raman spectroscopy, x-ray diffraction and selected area electron diffraction analysis. This approach enabled anatase-to-rutile phase transition hindering to be clearly observed for low Nb-doped TiO2 samples. Moreover, there was clear grain growth inhibition in the samples containing Nb. The use of high resolution transmission electron microscopy with our samples provides an innovative perspective compared with previous research on this issue. Our analysis shows that niobium is segregated from the anatase structure before and during the phase transformation, leading to the formation of NbO nanoclusters on the surface of the TiO2 rutile nanoparticles.