Modulation effect of microstructures in silicon-rich oxide matrix on photoluminescence from silicon nanoclusters prepared by different fabrication techniques

The modulation effect of microstructures on photoluminescence (PL) properties of silicon nanoclusters (Si NCs) in silicon-rich oxide (SRO) matrix prepared by electron-beam evaporation (EBE) and magnetron sputtering (MS) is investigated. A loose and porous microstructure is obtained from the SRO film prepared by EBE, while compact microstructure is acquired from that prepared by MS. The Si NCs with high density and good quality are formed in the SRO film prepared by EBE, and preferable PL performance of Si NCs is achieved in the EBE film with loose and porous microstructure. In contrast, the density and quality of Si NCs in the compact SRO film are suppressed and the PL properties are deteriorated due to the volumetric mismatching during the precipitation procedure of Si NCs. Optimization of the microstructures in SRO films should be made to reduce the volumetric mismatching and improve the PL properties of Si NCs.     

Influence of the temperature on the photoluminescence of silicon clusters embedded in a silicon oxide matrix

Amorphous silicon oxide thin films were prepared by co-evaporation of Si and SiO in ultra-high vacuum. Different compositions were obtained by changing the evaporation rate of silicon. After thermal annealing treatments, the dissociation of the silicon oxide in pure silicon and silicon dioxide leads to the formation of silicon clusters embedded in a silicon oxide matrix. Thus the samples were annealed to different temperatures up to 950°C. Depending on the annealing temperature and on the composition, different cluster sizes were obtained. The photoluminescence (PL) energy depends on the cluster size and a large range of wavelengths is obtained from 500 to 750 nm. The PL, attributed to a confinement effect of the electron–hole pairs in the silicon particles, is studied as a function of the temperature. It is demonstrated that the continuous decrease of PL intensity with the temperature from 77 to 500 K depends on the structure of the samples. For samples with well-separated clusters, the PL decreases rapidly with the temperature. For samples containing clusters separated by a small distance, the PL weakly depends on the temperature. No shift of the energy is observed. The results are discussed by taking into account the competition between the radiative recombination in the silicon clusters and the non-radiative escape of the carriers via a hopping mechanism.     

Structural and photoluminescence properties of ZnO nanoparticles on silicon oxide

Isolated, self assembled ZnO nanoparticles are grown in two steps: by the electron beam evaporation of Zn on oxidised silicon wafers, during which isolated Zn nanodots are grown, and a subsequent annealing in oxygen that results in the desired ZnO nanodots. Low temperature PL measurements of the ZnO nanodots show that the near band edge part of the spectra is dominated by a zero phonon line near 3.36 eV which is an overlap of two emitting lines near 3.363 eV and 3.367 eV. Characterization by TEM and EELS shows that the nanoparticles are zinc oxide single crystals grown with their c-axis perpendicular to the substrate; their distribution, size and crystallinity depend on the deposition parameters of zinc and the growth substrate. We discuss the effect of these parameters on the morphology of the resulting material. Our approach demonstrates a simple method for the growth of high purity isolated ZnO nanodots of similar sizes, distributed uniformly on a large surface. PACS 61.46.Df; 81.05.Dz; 81.07.-b     

Modeling the influence of the porosity of laser-ablated silicon films on their photoluminescence properties

Nanostructured porous Si-based films produced by pulsed laser ablation (PLA) from a silicon target in residual helium gas can exhibit both size-dependent (1.6-3.2 eV) and fixed photoluminescent (PL) bands (1.6 and 2.2 eV) with their relative contributions depending on the film porosity. We study the influence of prolonged oxidation in ambient air on properties of the fixed PL bands, associated with oxidation phenomena, and their correlation with structural properties of the films. In addition, we propose a model describing the appearance of surface radiation states for oxidized films of various porosities. Our experiments and numerical simulations led to a conclusion that the 1.6 eV PL is due to a mechanism involving a recombination through the interfacial layer between Si core and an upper oxide of nanocrystals. This mechanism gives the optimal porosity of 73% for the most efficient production of 1.6 eV PL centers that is in excellent agreement with our experimental results.     

Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in a silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embedded in a SiO 2 matrix is compared with that of unpassivated Si NCs. We investigate the relative enhancement of PL intensity (I R ) as a function of annealing temperature and implanted Si ion dose. The I R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization varying via the annealing temperature. The increase in I R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

Model of photoluminescence from ion-synthesized silicon nanocrystal arrays embedded in a silicon dioxide matrix

A four-level model of photoluminescence from Si nanocrystal arrays embedded in a SiO₂ matrix is suggested. The model allows for thermally activated transitions between singlet and triplet levels in the exchange-split energy state of an exciton in an excited silicon nanocrystal. An expression is derived for the temperature dependence of the intensity of photoluminescence monochromatic components. A correlation is found between the amount of splitting and the emitted photon energy by comparing model data with our experimental data for ion-synthesized Si nanocrystals in a SiO₂ matrix. The model explains the finiteness of the photoluminescence intensity at temperatures close to 0 K and the nonmonotonicity of the temperature run of the intensity.     

Effect of surface Si-Si dimers on photoluminescence of silicon nanocrystals in the silicon dioxide matrix

The effect of surface states of silicon nanocrystals embedded in silicon dioxide on the photoluminescent properties of the nanocrystals is reported. We have investigated the time-resolved and stationary photoluminescence of silicon nanocrystals in the matrix of silicon dioxide in the visible and infrared spectral ranges at 77 and 300 K. The structures containing silicon nanocrystals were prepared by the high-temperature annealing of multilayer SiO _x /SiO₂ films. The understanding of the experimental results on photoluminescence is underlain by a model of autolocalized states arising on surface Si-Si dimers. The emission of autocatalized excitons is found for the first time, and the energy level of the autolocalized states is determined. The effect of these states on the mechanism of the excitation and the photoluminescence properties of nanocrystals is discussed for a wide range of their dimensions. It is reliably shown that the cause of the known blue boundary of photoluminescence of silicon nanocrystals in the silicon dioxide matrix is the capture of free excitons on autolocalized surface states.     

Depth dependence of photoluminescence and chemical bonding in porous silicon

Porous silicon (PS) is studied by stepwise peeling of the surface layer to clarify the non-uniformity in the photoluminescence (PL) and correlate it with the in-depth chemical bonding and structure of the 30 μm thick layer. The PL intensity grows by an order of magnitude after the peeling off of the first 10 μm and decreases five times in the next 5 μm while the peak maximum position shifts from 730 to 800 nm. X-ray photoelectron spectroscopy (XPS) measurements show that Si–Si and Si–O bonds are present both on the surface and below, and the preferential oxidation state of silicon changes from 3+ and 4+ on the surface to 1+ and 2+ below 10 μm. Using Raman spectroscopy silicon nanocrystals are shown to exist. Their mean size can be estimated at about 3 nm. These results show that the strongest PL comes from a region in the PS layer where silicon nanocrystallites are surrounded by oxides with a low level of oxidation and not from the strongly oxidized surface layer.     

Structural and photoluminescence properties of silicon nanocrystals embedded in SiC matrix prepared by magnetron sputtering

Si nanocrystals (NCs) embedded in an SiC matrix were prepared by the deposition of Si-rich Si_1?xC_x/SiC nanomultilayer films using magnetron sputtering, subsequently followed by thermal annealing in the range of 800～1200 °C. As the annealing temperature increases to 1000 °C, Si NCs begin to form and SiC NCs also start to emerge at the annealing temperature of 1200 °C. With the increase of annealing temperature, two photoluminescence (PL) peaks have an obvious redshift. The intensity of the low-energy PL peak around 669～742 nm gradually lowers, however the intensity of high-energy PL peak around 601～632 nm enhances. The low-energy PL peak might attribute to dangling bonds in amorphous Si (a-Si) sublayers, and the redshift of this peak might be related to the passivation of Si dangling bonds. Whereas the origin of the high-energy PL peak may be the emergence of Si NCs, the redshift of this peak correlates with the change in the size of Si NCs.     

Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embeded in an SiO₂ matrix is compared with that of unpassivated ones. We investigate the relative enhancement of PL intensity (I_R) as a function of annealing temperature and implanted Si ion dose. The I_R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization via varying the annealing temperature. The increase in I_R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

Visible photoluminescence from silicon nanoclusters embedded in silicon nitride films prepared by remote plasma-enhanced chemical vapor deposition

The photoluminescence (PL) of silicon nanoclusters embedded in silicon nitride films grown by remote plasma-enhanced chemical vapor deposition at 200 °C, using mixtures of SiCl₄/H₂/Ar/NH₃ is investigated. It was found that the color and the intensity of the PL of the as-grown samples depend on the H₂ flow rate, and there is an optimum flow for which a maximum luminescence is obtained. A strong improvement of the PL intensity and change in color was obtained with annealing treatments in the range of 500–1000 °C. The changes in the composition, structure and optical properties of the films, as a function of H₂ flow rate and thermal treatments, were studied by means of Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry and ultraviolet–visible transmission measurements. We conclude that the PL can be attributed to quantum confinement effect in silicon nanoclusters embedded in silicon nitride matrix, which is improved when a better passivation of the nanoclusters surface is obtained.     

Morphological, structural, and magnetic properties of Co nanoparticles in a silicon oxide matrix

We present a morphological, structural, and magnetic characterization of Co nanoparticles (mean diameter of 10.3 ± 1.8 nm) grown using a gas aggregation source and embedded in a silicon oxide matrix by sequential deposition of nanoparticles and silicon oxide. We show that the Co nanoparticles ??soft-land?? on the substrates and suffer a moderate oxidation in contact with the silicon oxide. Despite this moderate oxidation, it is found that, at room temperature, the magnetic volume of the resulting nanoparticles is below the superparamagnetic limit. The results presented in this article are compatible with the presence of an assembly of magnetically independent particles that also display a moderate exchange bias at low temperature.     

Influence of LiBr on photoluminescence properties of porous silicon

A new method has been developed to improve the photoluminescence intensity of porous silicon (PS), which is first time that LiBr is used for passivation of PS. Immersion of the PS in a LiBr solution, followed by a thermal treatment at 100 °C for 30 min under nitrogen, leads to a nine fold increase in the intensity of the photoluminescence. The atomic force microscope (AFM) shows an increase of the nanoparticle dimension compared to the initial dimension of the PS nanostructure. The LiBr covers the nanoparticles of silicon without changing the wavelength distribution of the optical excitation and emission spectra. Moreover, a significant decrease of reflectivity was observed for the wavelength in the range of 350-500 nm.     

Comparative investigation of photoluminescence of silicon wire structures and silicon oxide films

Photoluminescence spectra and their dependence on temperature as well as Raman scattering spectra and Atomic Force Microscopy investigations have been used to study the peculiarities of the red photoluminescence band in low-dimensional Si structures, such as porous silicon and silicon oxide films. It has been shown that the red photoluminescence band of porous silicon is complex and can be decomposed into two elementary bands. It was discovered that elementary band intensities depend very much on surface morphology of porous silicon. The same positions of the photoluminescence bands are also observed in silicon oxide films for different oxide composition. Comparative investigation of the PL temperature dependences in porous silicon and silicon oxide films indicates that silicon-oxide defect related mechanisms of some elementary photoluminescence bands are involved.     

Effects of thermal oxidation on the photoluminescence properties of porous silicon

The effects of thermal oxidation on the photoluminescence (PL) properties of powdered porous silicon (PSi) are studied using X-ray photoelectron spectroscopy (XPS). It is found that the PL intensity is steeply quenched after annealing at and recovered at above . The XPS intensity of oxides formed on the PSi surface is also found to strongly depend on the annealing temperature. The comparison between the annealing temperature dependence of PL intensity and that of the oxide XPS intensity suggests that the formation of thin disordered SiO₂ layer accompanies the quenching of the PL intensity, and that the formation of thick high-quality SiO₂ layer results in the PL intensity recovery. These results indicate that the thickness and quality of SiO₂ layer play a crucial role in the PL properties of thermally oxidized PSi.     

Variation of spark-processing parameters on the photoluminescence properties of spark-processed silicon

Electrical and physical parameters, which influence the photoluminescence (PL) properties of spark-processed silicon (sp-Si), were systematically varied in order to obtain optimal PL emission. Among these parameters are the average spark current, the pulse width of the spark events, the frequency of the pulses, the processing time, the electrode diameter, the distance between the electrodes, the spark-processing environment, and the gas ambient pressure. It was found that for optimal PL emission the processing current needs to be between 20 and 40 mA, and the pulse frequency of the sparks between 10 and 15 kHz. Further, the N₂/O₂ ratio of the processing environment needs to be about 7:3 and the ambient gas pressure and the processing time as large as feasible. The conditions that are favorable for green PL are a small pulse width, a small counter electrode diameter, a small gap between electrodes, a relatively large nitrogen concentration in the processing chamber, and a comparatively large spark frequency. In the opposite cases, a UV/blue PL is predominantly observed. The results are discussed in terms of various thermal effects on the resulting molecules or defects, which are believed to be important for the PL emission.     

Temperature dependence of photoluminescence from CdSe nanocrystals embedded in silica matrix

In this work, CdSe nanocrystals (NCs) embedded in SiO₂ matrix were grown by radio frequency (RF)-sputtering technique. X-ray technique was used to characterise the structural properties of the system. The NC's size was estimated to be around 4±1 nm in diameter. The temperature dependence of the photoluminescence from the CdSe/SiO₂ system showed carriers thermal exchange between the NCs and deep defects in the matrix. The evolution of the excitonic energy emission with temperature is about 10 meV in the temperature range 15-295 K. This weak shift was explained by thermal mismatch between the matrix and the NCs.     

Control of the magnetic properties of silicon with manganese atom nanoclusters

It is found experimentally that the magnetic properties of a silicon matrix with manganese atom clusters can be controlled in wide ranges of magnetic and electric fields and temperature depending on the position of the Fermi level.     

Influence of the dielectric matrix on photoluminescence and energy exchange in ensembles of silicon nanocrystals

The results of a numerical simulation of photoluminescence in ensembles of Si nanocrystals incorporated into SiO₂ and ZrO₂ matrices are presented. It is shown that, in the ZrO₂ matrix, which produces a lower potential barrier for electrons and holes in nanocrystals, the photoluminescence intensity decreases significantly and the spectral peak shifts towards lower energies.     

Catalytic synthesis and photoluminescence of silicon oxide nanowires and nanotubes

A large quantity of nanowires and nanotubes of silicon oxide are produced by using Fe–Co–Ni alloy nanoparticles as catalyst. The products have a uniform diameter of around 100 nm. The nanowires have a smooth surface and the lengths are up to 100 μm or more. A new morphology called a serrated joint nanotube was found. The alloy catalyst plays a key role in the synthesis process. Room-temperature photoluminescence measurement under excitation at 360 nm showed that the silicon oxide had a strong blue-green emission at 525 nm (about 2.36 eV), which may be related to oxygen defects. PACS 81.15.Gh; 81.07.Vb; 81.07.De; 42.70.Nq; 78.55.-m