Defect passivation by hydrogen reincorporation for silicon quantum dots in SiC/SiOx hetero-superlattice

The SiC/SiO_x hetero-superlattice (HSL) consisting of alternating near-stoichiometric SiC barrier layers for the electrical transport and silicon rich SiO_x matrix layers for the quantum dot formation is a promising approach to the realization of silicon quantum dot (Si–QD) absorbers for 3rd generation solar cells. However, additional defect states are generated during post deposition annealing needed for the Si–QD formation causing an increase in sub-band gap absorption and a decrease in PL intensity. Proper passivation of excess defects is of major importance for both the optical and electrical properties of the SiC/SiO_x HSL Si–QD absorber. In this work, we investigate the effectiveness of the hydrogen reincorporation achieved with hydrogen plasma in a plasma-enhanced chemical vapor deposition (PECVD) reactor, hydrogen dissociation catalysis in hot-wire chemical vapor deposition (HWCVD) reactor and annealing in forming gas atmosphere (FGA). Both the HSL samples and single layer reference samples are tested. The passivation quality of the hydrogen reincorporation was examined by comparing electrical and optical properties measured after deposition, after annealing and after passivation. In addition, the formation of Si–QDs in SiC/SiO_x HSL was evaluated using high resolution transmission electron microscopy. We demonstrated that hydrogen can be successfully reincorporated into the annealed HSL sample and its single layer reference samples. FGA passivation is most effective for SiO_1.2 single layers and HSL samples. Passivation with PECVD appeared to be only effective for SiC single layers.     

Photoluminescence of Si or Ge nanocrystallites embedded in silicon oxide

This paper presents the results of photoluminescence, its temperature dependence and Raman scattering investigations on magnetron co-sputtered silicon oxide films with (or without) embedded Si (or Ge) nanocrystallites. It is shown the oxide related defect origin of the visible PL centers peaked at 1.7, 2.06 and 2.30 eV. The infrared PL band centered at 1.44–1.58 eV in Si–SiO_x, system has been analyzed within a quantum confinement PL model. Comparative PL investigation of Ge–SiO_x system has confirmed that high energy visible PL bands (1.60–1.70 and 2.30 eV) are connected with oxide related defects in SiO_x. The PL band in the spectral range of 0.75–0.85 eV in Ge–SiO_x system is attributed to exciton recombination inside of Ge NCs.     

Photoluminescence properties of erbium-doped structures of silicon nanocrystals in silicon dioxide matrix

We present a study of the photoluminescence (PL) of structures of Si nanocrystals (nc-Si) in erbium-doped amorphous silicon dioxide. It is shown that the energy of excitons confined in nc-Si of 2–5 nm sizes is efficiently transferred to Er³⁺ ions in surrounding SiO₂ and a strong PL line at 1.5 μm appears. At high excitation intensity the population inversion of Er³⁺ ion states is achieved. These results demonstrate good perspectives of Er-doped nc-Si/SiO₂ structures for possible applications in Si-based optical amplifiers and lasers.     

Effects of passivation and postannealing on the photoluminescence properties of MgO/SiO2 core‐shell nanorods

MgO nanorods were grown by the thermal evaporation of Mg₃N₂ powders on the Si (100) substrate coated with a gold thin film. The MgO nanorods grown on the Si (100) substrate were a few tens of nanometers in diameter and up to a few hundreds of micrometers in length. MgO/SiO₂ core‐shell nanorods were also fabricated by the sputter‐deposition of SiO₂onto the MgO nanorods. Transmission electron microscopy (TEM) and X–ray diffraction (XRD) analysis results indicated that the cores and shells of the annealed core‐shell nanorods were a face‐centered cubic‐type single crystal MgO and amorphous SiO₂, respectively. The photoluminescence (PL) spectroscopy analysis results showed that SiO₂ coating slightly decreased the PL emission intensity of the MgO nanorods. The PL emission of the MgO/SiO₂ core‐shell nanorods was, however, found to be considerably enhanced by thermal annealing and strongly depends on the annealing atmosphere. The PL emission of the MgO/SiO₂ core‐shell nanorods was substantially enhanced in intensity by annealing in a reducing atmosphere, whereas it was slightly enhanced by annealing in an oxidative atmosphere. The origin of the PL enhancement by annealing in a reducing atmosphere is discussed with the aid of energy‐dispersive X‐ray spectroscopy analyses. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Strong and stable red photoluminescence from porous silicon prepared by Fe-contaminated silicon

Strong red photoluminescence (PL) spectra appeared at porous silicon (PS) samples prepared by a chemical anodization of Fe-contaminated Si substrates. The Fe1000 sample with Fe contamination of 1000 ppb showed a ten times stronger red PL than that of the reference PS sample without any Fe contamination, and this sample also showed the higher thermal stability for PL spectra as compared with the reference PS sample. Furthermore, the PL intensity from the PS with Fe contamination is linearly proportional to the Fe-related trap concentrations of Si substrates obtained from DLTS. Especially, all the PS samples exhibit the same PL peak position regardless of Fe contamination concentrations, as compared with that of the reference PS. This means that there is no significant effect such as the variation of size distribution of nanocrystalline Si in PS layer formed on Fe-contaminated Si substrate. Based on the results of PL and DLTS, we found that the PL efficiency depends strongly on the Fe-related trap concentration in Si substrates.     

GaN-based nitride semiconductor films deposited on nitrified HfO2/Si substrate by molecular beam epitaxy

Nitrified HfO₂/Si substrate was used to grow GaN-based film with molecular beam epitaxy. Four-period InGaN/GaN layered structure and p/n junction were deposited on the nitrified HfO₂/Si. X-ray photoelectron spectroscopy (XPS) result shows that N was effectively incorporated into the HfO₂. The crystallographic relationship of the GaN/HfO₂/Si is GaN(0 0 0 2)∥HfO₂(1 1 1)∥Si(1 1 1). Temperature-dependent photoluminescence (PL), PL peak wavelength, PL peak intensity, and PL full-width at half-maximum of the p/n junction were investigated. Light-emitting diode was fabricated from the p/n junction. Red light was emitted at low voltage and yellow light was emitted when increasing the voltage.     

Growth of amorphous SiO2 nano-wires on pre-oxidized silicon substrate via chemical vapor deposition

Without an additional silicon source, amorphous SiO₂ nano-wires were grown on the pre-oxidized silicon substrate with the assistance of Ni-based catalyst under ambient pressure. The as-grown amorphous SiO₂ nano-wires were characterized by X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy (HRTEM) and selected area diffraction. The micro-region chemical composition investigation on the as-grown amorphous SiO₂ nano-wires was carried out using X-ray energy dispersion spectroscopy (EDS) on the HRTEM. The present work focuses on the formation of atomic H on the surface of pure zinc powder by introducing moisture (N₂ + H₂O) into the furnace at high temperature. The growth mechanism has been discussed and attributed to the vapor–liquid–solid (VLS) mechanism instead of the adopted solid–liquid–solid (SLS) mechanism owing to the observed evidence of an etching reaction of atomic H at the SiO₂ buffer layer and/or that of H at the Si substrate to form a gaseous hydro-silicon radical (SiH_x) that is then transported to the growth sites. The intrinsic luminescent behavior of the amorphous SiO₂ nano-wires in the range of 350–430 nm was also reported and discussed. These results provide an alternative and simple procedure for nanostructures growth, which will be helpful to understand the growth mechanism of one dimensional SiO₂ nanostructures.     

Structure and optical properties of light-emitting Si films fabricated by neutral cluster deposition and subsequent high-temperature annealing

As a new development of our previous study on the production of light-emitting amorphous Si (a-Si) films by the neutral cluster deposition (NCD) method, we have fabricated light-emitting Si films with improved emission intensity by the combined methods of NCD and subsequent high-temperature annealing. The structure of these films is best characterized by Si nanocrystals, surrounded by an interfacial a-SiO_x (x < 2) layer, embedded in an a-SiO₂ film. These improved Si films were observed by atomic force microscopy and high-resolution transmission electron microscopy, and analyzed by means of X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence (PL) and Fourier transform infrared-attenuated total reflection measurements. The PL curves of the annealed samples exhibit peaks around 600 nm, at almost the same position as the unannealed samples. Their PL intensities, however, have increased to approximately five times those of the unannealed samples. The source of the luminescence is most likely due to electron-hole recombination in the a-SiO₂/Si interfacial a-SiO_x layer.     

Photoluminescence of Si nanocrystallites in different types of matrices

This paper presents the comparative investigation of photoluminescence (PL) and its temperature dependence for rf-magnetron co-sputtered Si-enriched SiO_x systems and amorphous Si films prepared by hot-wire CVD method with Si nanocrystallites of different sizes. It is shown that PL spectra of Si–SiO_x films consist of the five PL bands peaked at 1.30, 1.50, 1.76, 2.05 and 2.32 eV. Amorphous Si films with Si nanocrystallites are characterized by three PL bands only peaked at 1.35, 1.50 and 1.76 eV. The peak position of the 1.50 eV PL band shifts with the change of Si quantum dot sizes and it is attributed to exciton recombination inside of Si quantum dots. The nature of four other PL bands is discussed as well.     

An electron diffraction study of amorphous silicon oxide films

Amorphous silicon oxide films have been examined by high energy electron diffraction using the sector-microphotometer method of data collection common to gas phase electron diffraction. This data was analyzed with a least-squares procedure that is designed to minimize extraneous detail in the radial distribution function obtained by the Fourier sine transform of the interference function. The results of this analysis for thin film SiO₂ show that the overall bonding topology of the thin film agress well with that of bulk (vitreous) SiO₂ examined by X-ray diffraction. The experimental short distance parameters for the films whose composition was determined to be ～SiO_1.3, SiO, and SiO_0.8 are found to be consistent with those expected for a mixture of tetrahedrally bonded amorphous Si and SiO₂ phases in which the scale of the Si-like and SiO₂-like regions is of the order of a few basic tetrahedral units. This result is in agreement with previous examinations of SiO powder by X-rays and a previous examination of thin silicon oxide films by electron diffraction.     

Melting and crystallization of silicon layers on insulator with millisecond lamp heating

Melting and crystallization of silicon layers in a SOI structure (Si SiO₂ Si) at millisecond lamp heating have been studied by model calculations using the solution of conduction equation. Pulse heating conditions that do not lead to silicon substrate melting under SiO₂ have been determined. For pulses of 1 and 4.4 ms duration the silicon melt lifetime on the SiO₂ surface has been estimated. The lengths of the crystal oriented growth from windows in the SiO₂ layer that open the single-crystalline silicon substrate have been measured (25 and 64 μm).     

Noncrystalline silicon dioxide films on silicon: A review

Firstly, the importance of noncrystalline SiO₂ film in the manufacture of semiconductor devices and integrated circuits is pointed out. After some general remarks on the SiSiO₂ interface, various methods of preparing SiO₂ films on silicon are discussed with emphasis on thermal oxidation of silicon. The transport processes are compared with those occurring in fused silica. Then, the properties of the SiSiO₂ interface structure are summarized; a properly prepared interface is very perfect. This is due to the structural flexibility of noncrystalline SiO₂. Finally, the structural aspects of noncrystalline SiO₂ are discussed on the basis of the chemistry of the SiO bond in which the π component plays a special role. The high degree of short-range order is responsible for many excellent properties of the oxide film. Disruption of the short-range order results in network defects and development of some degree of local order along a direction which it is assumed to give rise to channels. These defects are unique to topologically disordered solids. In this and many other respects, noncrystalline SiO₂ is more similar to siloxane polymers than typical ionic or covalent crystals.     

Composition of Ge+ and Si+ implanted SiO2/Si layers: Role of oxides in nanocluster formation

X-ray photoelectron spectroscopy (XPS) has been used to examine the atomic content of implanted SiO₂/Si layers. In particular, an XPS analysis permits to identify elemental Ge and Si, as well as GeO₂ precipitations in SiO₂ matrices. The XPS results reveal valuable information not only about the formation mechanism of Ge and Si nanoclusters but also on the annealing kinetics of SiO₂ whose properties are known to be significantly altered during the process of ion implantation and subsequent annealing. The composition of ion beam-modified SiO₂ layers strongly depends on the annealing temperature. With respect to germanium implanted samples a possibility of Ge nanocrystals formation appears at high (above 1000 °C) annealing temperatures. It has been shown that an intermediate step in the Ge oxide formation is necessary for the creation of Ge nanoclusters. Additionally, the presence of a subsurface zone GeO_x (about 100 nm thick) predicted in kinetic three-dimensional lattice simulations has been confirmed. In the case of Si⁺ implanted samples substoichiometric silicon oxide lines in the XPS spectra of a SiO₂ layer for all samples have been observed. No evidence of a line connected to the Si–Si bonding has been observed even at the highest annealing temperatures, at which only stoichiometric SiO₂ has been detected.     

Reflectivity measurements of thin SiO2 layers in the soft-X-ray region

Energy and angular dependent reflectivity measurements of differently prepared SiO₂ layers were made in the soft X-ray region in order to study differences in their optical and electronic behaviour caused by the technological process. The optical constants of the layers were determined by fitting the angular dependent reflectivity data with a multilayer model which takes into account the roughness of all interfaces. Detailed knowledge of the polarization level of the primary beam from the synchrotron radiation source is needed for reliable results. The energy dependent reflectivity measurements indicate that high-pressure dry-oxidized layers have a more perfect structure than normal dry-oxidized layers. Independent on the deposition process the Si SiO₂ interface roughness amounts to ± 1 nm. The Si_2p-XANES of Si and SiO₂ were detected.     

Development of porous silicon matrix and characteristics of porous silicon/tin oxide structures

Porous silicon (PSi) was formed at different current densities in the range of 5-60 mA/cm² by electrochemical anodized etching in HF for different durations in the range of 10-30 min. Above this PSi structure, SnO₂ films were deposited by the spin coating technique. The PSi has been characterized by X-ray diffraction studies. Peaks pertaining to PSi along with those corresponding to SnO₂ are observed. Atomic force microscopic studies indicate that very fine needle like silicon nanostructures are observed which is the result of the best PSi structure formed at 30 mA/cm². For the SnO₂ covered PSi structures, larger grains are observed with uniform coverage. The PSi samples prepared at current densities above and below 30 mA/cm² show PL spectra with asymmetric and overlapped peaks. The PL profile of thin SnO₂ film coated on PSi shows a peak at 633 nm and a small hump at about 660 nm.     

Fabrication of (1 1 1)-oriented Si layers on SiO2 substrates by an aluminum-induced crystallization method and subsequent growth of semiconducting BaSi2 layers for photovoltaic application

We have prepared (1 1 1)-oriented Si layers on SiO₂ (fused silica) substrates from amorphous-Si(a-Si)/Al or Al/a-Si stacked layers using an aluminum-induced crystallization (AIC) method. The X-ray diffraction (XRD) intensity from the (1 1 1) planes of Si was found to depend significantly on growth conditions such as the thicknesses of Si and Al, deposition order (a-Si/Al or Al/a-Si on SiO₂), deposition technique (sputtering or vacuum evaporation) and exposure time of the Al layer to air before the deposition of Si. The crystal orientation of the Si layers was confirmed by θ−2θ, 2θ XRD and electron backscatter diffraction (EBSD). The photoresponse properties of semiconducting BaSi₂ films formed on the (1 1 1)-oriented Si layers by the AIC method were measured at room temperature. Photocurrents were clearly observed for photon energies greater than 1.25 eV. The external quantum efficiencies of the BaSi₂ were also evaluated.     

Rapid crystallization of amorphous silicon utilizing a radio-frequency thermal plasma torch

The rapid crystallization of amorphous silicon utilizing the radio-frequency (rf) inductive coupling thermal plasma torch of argon is demonstrated. Highly-crystallized Si films were fabricated on thermally grown (th-)SiO₂ and textured a-Si:H:B/SnO₂/glass by adjusting a distance between the tip of the silica tube and the substrate stage and the translational velocity of the substrate stage. The crystallization was promoted efficiently from the bottom to front surface during the solidification and crystallization of liquid Si.     

Role of ballistic transport in photoluminescence excitation of Si nanocrystals

Photoluminescence of Si NCs with the size (10–300 nm) bigger than the exciton Bohr radius in the bulk Si crystals (4.8 nm) has been considered. Photoluminescence in such NC systems is analyzed from the point of view of new concept based on the effect of hot carrier ballistic transport in excitation of suboxide defect-related photoluminescence at the Si/SiO_x interface. The dependence of the 1.70 eV PL band integrated intensity on Si NC sizes was numerically calculated on the base of the hot carrier ballistic PL model. The well correlation between calculated and experimental results has been obtained for Si NCs with the size from the 30–150 nm range.     

High resolution 29Si NMR study of the structure and devitrification of lead-silicate glasses

High speed magic-angle rotation of glass samples in the strong polarizing field of a superconducting magnet yields high-resolution ²⁹Si NMR spectra. Using this technique glasses of various composition, PbO·SiO₂, (PbO)₂·SiO₂, and (PbO)₄·SiO₂ were studied and the influence of thermal treatment followed. Crystallization of PbO·SiO₂ glass has been found to be a complex process leading to a structure identical with that of the mineral alamosite. The ²⁹Si NMR spectrum of crystalline alamosite consists of three lines in agreement with the structure determined by X-ray diffraction.     

Synthesis by sol–gel process,characterization and catalytic activity of vanadia–silica mixed oxides

This paper describes a new route for the preparation of V₂O₅–SiO₂ mixed oxides with high vanadium content and high surface area by the sol–gel processing method. Dry samples were characterized by powder X-ray diffraction, electron paramagnetic resonance, Fourier-transform infrared, and energy dispersive X-ray spectrometry. Our results show that the incorporation of vanadium pentoxide into the silica matrix was obtained by intimate mixing of the two different inorganic polymers (Si–O and V–O based polymers), and the overall structure is held together by a Si–O–Si network interpenetrated with V–O–V polymeric chains. The catalytic activity of the V₂O₅–SiO₂ mixed oxides was evaluated in the oxidation of the cyclooctene and styrene in liquid phase.