Structural and optical properties of Si/SiO2 multi-quantum wells

Structural and optical properties of Si/SiO₂ multi-quantum wells (MQW) were investigated by means of Raman scattering and photoluminescence (PL) spectroscopy. The MQW structures were fabricated on a quartz substrate by remote plasma enhanced chemical vapour deposition (RPECVD) of alternating amorphous Si and SiO₂ layers. After layer deposition the samples were subjected to heat treatments, i.e. rapid thermal annealing (RTA) and furnace annealing. Distinct PL signatures of confined carriers evidenced formation of Si-nanocrystals (nc-Si) in annealed samples. Analyses of Raman spectra also show presence of nc-Si phase along with amorphous-Si (a-Si) phase in the samples. The strong influence of the annealing parameters on the formation of nc-Si phase suggests broad possibilities in engineering MQW with various optical properties. Interestingly, conversion of the a-Si phase to the nc-Si phase saturates after certain time of furnace annealing. On the other hand, thinner Si layers showed a disproportionately lower crystalline volume fraction. From the obtained results we could assume that an interface strain prevents full crystallization of the Si layers and that the strain is larger for thinner Si layers. The anomalous dependence of nc-Si Raman scattering peak position on deposited layer thickness observed in our experiments also supports the above assumption.     

Nanostructuring Si surface and Si/SiO2 interface using porous-alumina-on-Si template technology. Electrical characterization of Si/SiO2 interface

In this work, anodic porous alumina thin films with pores in the nanometer range are grown on silicon by electrochemistry and are used as masking material for the nanopatterning of the silicon substrate. The pore diameter and density are controlled by the electrochemical process. Through the pores of the alumina film chemical oxidation of the silicon substrate is performed, leading to the formation of regular arrays of well-separated stoichiometric silicon dioxide nanodots on silicon, with a density following the alumina pores density and a diameter adjustable by adjusting the chemical oxidation time. The alumina film is dissolved chemically after the SiO₂ nanodots growth, revealing the arrays of silicon dioxide dots on silicon. In a next step, the nanodots are also removed, leaving a nanopatterned bare silicon surface with regular arrays of nanopits at the footprint of each nanodot. This silicon surface structuring finds interesting applications in nanoelectronics. One such application is in silicon nanocrystals memories, where the structuring of the oxidized silicon surface leads to the growth of discrete silicon nanocrystals of uniform size. In this work, we examine the electrical quality of the Si/SiO₂ interface of a nanostructured oxidized silicon surface fabricated as above and we find that it is appropriate for electronic applications (an interface trap density below 1–3×10¹⁰ eV⁻¹ cm⁻² is obtained, indicative of the high quality of the thermal silicon oxide).     

Further indication of a low quartz structure at the SiO2/Si interface from coincidence Doppler broadening spectroscopy

Results from coincidence Doppler broadening (CDB) measurements on various Si samples and Brazilian quartz having low quartz structure are presented with the aim to give further strong indication of the existence of a low quartz structure, but not of Si divacancies as frequently considered, at the SiO₂/Si interface.     

Room temperature visible light emission from Si/SiO2 multilayers: Roles of interface electronic states and silicon phase

We have studied luminescence properties and microstructure of 20 patterns Si/SiO₂ multilayers. The photoluminescence spectra consist of two gaussian bands in the visible-infrared spectral region. It has been demonstrated that the strong PL band is caused by the radiative recombination in the Si/SiO₂ interfaces states, whereas the weaker band originates from radiative recombination in the nanosized Si layers. The peak shift of this latter band shows a discontinuity that corresponds to a crystalline-to-amorphous phase change when the Si layers are thinner than 30 Å. The peak energy as a function of the layer thickness is interpreted using a quantum confinement model in the case of amorphous Si layers.     

Influence of SiO2 additional layers on the laser induced damage threshold of Ta2O5 films

A series of Ta₂O₅ films with different SiO₂ additional layers including overcoat, undercoat and interlayer was prepared by electron beam evaporation under the same deposition process. Absorption of samples was measured using the surface thermal lensing (STL) technique. The electric field distributions of the samples were theoretical predicted using thin film design software (TFCalc). The laser induced damage threshold (LIDT) was assessed using an Nd:YAG laser operating at 1064 nm with a pulse length of 12 ns. It was found that SiO₂ additional layers resulted in a slight increase of the absorption, whereas they exerted little influence on the microdefects. The electric field distribution among the samples was unchanged by adding an SiO₂ overcoat and undercoat, yet was changed by adding an interlayer. SiO₂ undercoat. The interlayer improved the LIDT greatly, whereas the SiO₂ overcoat had little effect on the LIDT.     

Substrate temperature dependence of the photoluminescence efficiency of co-sputtered Si/SiO2 layers

Si particles embedded in an SiO₂ matrix were obtained by co-sputtering of Si and SiO₂ at various deposition temperatures T_d (200–700°C) and annealing at different temperatures T_a (900–1100°C). The systems were characterized by X-ray photoelectron, Raman scattering, infrared absorption and photoluminescence spectroscopy techniques. The results show that the photoluminescence efficiency is strongly dependent on the degree of phase separation between the Si nanocrystals and the SiO₂ matrix. This is likely connected with the Si/SiO₂ interface characteristics, together with the features indicating the involvement of quantum confinement.     

Effects of deposition rates on laser damage threshold of TiO2/SiO2 high reflectors

TiO₂ single layers and TiO₂/SiO₂ high reflectors (HR) are prepared by electron beam evaporation at different TiO₂ deposition rates. It is found that the changes of properties of TiO₂ films with the increase of rate, such as the increase of refractive index and extinction coefficient and the decrease of physical thickness, lead to the spectrum shift and reflectivity bandwidth broadening of HR together with the increase of absorption and decrease of laser-induced damage threshold. The damages are found of different morphologies: a shallow pit to a seriously delaminated and deep crater, and the different amorphous-to-anatase-to-rutile phase transition processes detected by Raman study. The frequency shift of Raman vibration mode correlates with the strain in film. Energy dispersive X-ray analysis reveals that impurities and non-stoichiometric defects are two absorption initiations resulting to the laser-induced transformation.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.     

Si/SiO2 multilayers: synthesis by reactive magnetron sputtering and photoluminescence emission

This paper relates a complete study of Si/SiO₂ multilayer (ML) structures. First, we suggest an original way of synthesis based on reactive magnetron sputtering of a pure silica target. The photoluminescence spectra of these MLs consist of two Gaussian bands in the visible-near infrared spectral region. The stronger one (I band) is fixed at about 780 nm and probably due to interface states. The weaker one (Q band) is tuneable with the Si sublayer thickness and originates from a radiative recombination within the nanosized Si layers. For this latter band the peak position is a function of the Si sublayer thickness and shows a discontinuity at 30 Å. This corresponds to an Si phase change. For thicknesses above 30 Å, the sublayers are composed of nanocrystalline silicon whereas below 30 Å the sublayers are made of amorphous silicon. We develop a model based on a quantum well to which we have added an interfacial region between Si and SiO₂. It is characterised by an interfacial potential of 0.3 eV. This model depicts the simultaneous behaviour of Q and I bands for an Si sublayer thickness below 30 Å.     

Anneal temperature dependence of Si/SiO2 superlattices photoluminescence

Photoluminescence spectroscopy, Fourier transform infrared spectroscopy, X-ray reflectometry and high resolution electron microscopy have been used to interpret the photoluminescence properties of annealed (3/19 nm) Si/SiO₂ multilayers grown by reactive magnetron sputtering. The multilayers show an emission in the visible and near-infrared range after heat treatment from 900°C which tends to decrease from 1200°C. Three different origins for the photoluminescence activity have been found. An anneal temperature of 1200°C is necessary to optimise the silicon crystallisation within the silicon sublayers.     

Influence of patterning on the nucleation of Ge islands on Si and SiO2 surfaces

Surface patterning is expected to influence the nucleation site of deposited nanostructures. In the present study, clean Si and SiO₂ surfaces were patterned by a nanolithographic process using a Focused Ion Beam (FIB). Ge was evaporated in ultra high vacuum at 873 K on these substrates, resulting in the formation of island arrays. Based on scanning tunneling microscopy and atomic force microscopy images, a statistical analysis was performed in order to highlight the effect of patterning on the size distribution of islands compared to a non-patterned surface. We find that the self-organization mechanism on patterned substrates results in a very good arrangement and positioning of Ge nanostructures, depending on growth conditions and holes distance, both on Si and SiO₂ surfaces.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.     

Silicon nanoparticles formation in annealed SiO/SiO2 multilayers

We present a study on amorphous SiO/SiO₂ superlattice performed by grazing-incidence small-angle X-ray scattering (GISAXS). Amorphous SiO/SiO₂ superlattices were prepared by high-vacuum evaporation of 3 nm thin films of SiO and SiO₂ (10 layers each) onto Si(1 0 0) substrate. After the deposition, samples were annealed at 1100 °C for 1 h in vacuum, yielding to Si nanocrystals formation. Using a Guinier approximation, the shape and the size of the crystals were obtained. The size of the growing nanoparticles in the direction perpendicular to the film surface is well controlled by the bilayer thickness. However, their size varies more significantly in the direction parallel to the film surface.     

Photoluminescence of colloidal YVO4:Eu/SiO2 core/shell nanocrystals

YVO₄:Eu, and YVO₄:Eu/SiO₂ nanocrystals (NCs) were prepared by hydrothermal method with citrate as capping ligands. Their morphologies, structures, components, and photoluminescence properties were investigated and presented in this paper. A remarkable fluorescence enhancement up to 2.17 times was observed in colloidal YVO₄:Eu/SiO₂ NCs, compared to that of colloidal YVO₄:Eu NCs. This is mainly attributed to the formation of the outer protecting layers of biocompatible SiO₂ shells; which shield the Eu³⁺ ions effectively from water and thus reduces the deleterious effects of water on the luminescence. Meanwhile, on the basis of laser selective excitation, two kinds of luminescent centers were confirmed in the NCs, namely, inner Eu³⁺ ions and surface Eu³⁺ ions. The surface modifications for YVO₄:Eu NCs effectively reduced the surface defects and accordingly enhanced the luminescence. The core/shell NCs exhibited long fluorescence lifetime and high photostability under ultraviolet radiation.     

Deposition and characterization of binary Al2O3/SiO2 coating layers on the surfaces of rutile TiO2 and the pigmentary properties

Binary Al₂O₃/SiO₂-coated rutile TiO₂ composites were prepared by a liquid-phase deposition method starting from Na₂SiO₃·9H₂O and NaAlO₂. The chemical structure and morphology of binary Al₂O₃/SiO₂ coating layers were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, TG-DSC, Zeta potential, powder X-ray diffraction, and transmission electron microscopy techniques. Binary Al₂O₃/SiO₂ coating layers both in amorphous phase were formed at TiO₂ surfaces. The silica coating layers were anchored at TiO₂ surfaces via Si-O-Ti bonds and the alumina coating layers were probably anchored at the SiO₂-coated TiO₂ surfaces via Al-O-Si bonds. The formation of continuous and dense binary Al₂O₃/SiO₂ coating layers depended on the pH value of reaction solution and the alumina loading. The binary Al₂O₃/SiO₂-coated TiO₂ composites had a high dispersibility in water. The whiteness and brightness of the binary Al₂O₃/SiO₂-coated TiO₂ composites were higher than those of the naked rutile TiO₂ and the SiO₂-coated TiO₂ samples. The relative light scattering index was found to depend on the composition of coating layers.     

Influence of overcoat on laser-induced damage threshold of 532 and 800 nm TiO2/SiO2 high reflectors

TiO₂/SiO₂ high reflectors with and without a SiO₂ overcoat are deposited by electron-beam evaporation. The film properties are characterized by visible spectrometry measures, structure analysis, roughness and laser-induced damage threshold (LIDT) tests, surface defects and damage morphology observation. The effects of overcoats on LIDT at 532 nm, 8 ns and 800 nm, 220 ps laser pulses are investigated. The relations between film structure, roughness, surface defects, electric field and LIDT are discussed. It is found that overcoats can increase the LIDT at these two laser wavelengths. The reduction of peak temperature, the low defects density and roughness, the low intrinsic absorption of SiO₂ and its amorphous structure are the main reasons for LIDT improvement by overcoats.     

Tunable photoluminescence and electroluminescence of size-controlled silicon nanocrystals in nanocrystalline-Si/SiO2 superlattices

We present photoluminescence and electroluminescence of silicon nanocrystals deposited by plasma-enhanced chemical vapor deposition (PECVD) using nanocrystalline silicon/silicon dioxide (nc-Si/SiO₂) superlattice approach. This approach allows us to tune the nanocrystal emission wavelength by varying the thickness of the Si layers. We fabricate light emitting devices (LEDs) with transparent indium tin oxide (ITO) contacts using these superlattice materials. The current-voltage characteristics of the LEDs are measured and compared to Frenkel-Poole and Fowler-Nordheim models for conduction. The EL properties of the superlattice material are studied, and tuning, similar to that of the PL spectra, is shown for the EL spectra. Finally, we observe the output power and calculate the quantum efficiency and power conversion efficiency for each of the devices.     

Analysis of excimer laser annealing of amorphous SiGe on La2O3//Si structures

The reduction of complementary metal oxide semiconductor dimensions through transistor scaling is in part limited by the SiO₂ dielectric layer thickness. Among the materials evaluated as alternative gate dielectrics one of the leading candidate is La₂O₃ due to its high permittivity and thermodynamic stability. However, during device processing, thermal annealing can promote deleterious interactions between the silicon substrate and the high-k dielectric degrading the desired oxide insulating properties.The possibility to grow poly-SiGe on top of La₂O₃//Si by laser assisted techniques therefore seems to be very attractive. Low thermal budget techniques such as pulsed laser deposition and crystallization can be a good choice to reduce possible interface modifications due to their localized and limited thermal effect.In this work the laser annealing by ArF excimer laser irradiation of amorphous SiGe grown on La₂O₃//Si has been analysed theoretically by a numerical model based on the heat conduction differential equation with the aim to control possible modifications at the La₂O₃//Si interface. Simulations have been carried out using different laser energy densities (0.26-0.58 J/cm²), different La₂O₃ film thickness (5-20 nm) and a 50 nm, 30 nm thick amorphous SiGe layer. The temperature distributions have been studied in both the two films and substrate, the melting depth and interfaces temperature have been evaluated. The fluences ranges for which the interfaces start to melt have been calculated for the different configurations.Thermal profiles and interfaces melting point have shown to be sensitive to the thickness of the La₂O₃ film, the thicker the film the lower the temperature at Si interface.Good agreement between theoretical and preliminary experimental data has been found.According to our results the oxide degradation is not expected during the laser crystallization of amorphous Si_0.7Ge_0.3 for the examined ranges of film thickness and fluences.     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

First-principles study of the segregation of boron dopants near the interface between crystalline Si and amorphous SiO2

We investigate the stability of boron dopants near the interface between crystalline Si and amorphous SiO₂ through first-principles density functional calculations. An interstitial B is found to be more stable in amorphous SiO₂ than in Si, so that B dopants tend to segregate to the interface. When defects exist in amorphous SiO₂, the stability of B is greatly enhanced, especially around Si floating bond defects, while it is not significantly affected near Si–Si dimers, which are formed by O-vacancy defects.