Carbothermal reduction and nitridation reaction of SiOx and preoxidized SiOx: Formation of α-Si3N4 fibers

The chemical composition of amorphous SiOx has been analyzed by oxidation studies and is found to be SiO1.7. SiO1.7 appears to be a monophasic amorphous material on the basis of 29Si nuclear magnetic resonance, high resolution electron microscopy, and comparative behavior of a physical mixture of Si and SiO2. Carbothermal reduction and nitridation reactions have been carried out on amorphous SiO1.7 and on amorphous SiO2 obtained from oxidation of SiO1.7. At 1623 K reactions of SiO1.7 lead exclusively to the formation of Si2N2O, while those of SiO2 lead exclusively to the formation of Si3N4. Formation of copious fibers of α-Si3N4 was observed in the latter reaction. It is suggested that the partial pressure of SiO in equilibrium with reduced SiO1.7 and SiO2 during the reaction is the crucial factor that determines the chemistry of the products. The differences in the structures of SiO2 and SiO1.7 have been considered to be the origin of the differences in the SiO partial pressures of the reduction products formed prior to nitridation. The effect of the ratios, C:SiO1.7 and C:SiO2, in the reaction mixture as well as the effect of the temperature on the course of the reactions have also been investigated.

Microstructural evolution of SiOx films and its effect on the luminescence of Si nanoclusters

In this paper we demonstrate that the structural and optical properties of Si nanoclusters (Si ncs) formed by thermal annealing of SiOx films prepared by plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering are very different. In fact, at a fixed Si excess and annealing temperature, photoluminescence (PL) spectra of sputtered samples are redshifted with respect to PECVD samples, denoting a larger Si ncs size. In addition, PL intensity reaches a maximum in sputtered films at annealing temperatures much lower than those needed in PECVD films. These data are correlated with structural properties obtained by energy filtered transmission electron microscopy and electron energy loss spectroscopy. It is shown that in PECVD films only around 30% of the Si excess agglomerates in clusters while an almost complete agglomeration occurs in sputtered films. These data are explained on the basis of the different initial structural properties of the as-deposited films that become crucial for the subsequent evolution. © 2008 American Institute of Physics.

Evolution of structural defects in SiOx films fabricated by electron cyclotron resonance plasma chemical vapour deposition upon annealing treatment

We study the structural defects in the SiOx film prepared by electron cyclotron resonance plasma chemical vapour deposition and annealing recovery evolution. The photoluminescence property is observed in the as-deposited and annealed samples. [-SiO3](2-) defects are the luminescence centres of the ultraviolet photoluminescence (PL) from the Fourier transform infrared spectroscopy and PL measurements. [-SiO3](2-) is observed by positron annihilation spectroscopy, and this defect can make the S parameters increase. After 1000 degrees C annealing, [-SiO3](2-) defects still exist in the films.

Enhanced charge storage characteristics of silicon nanocrystals fabricated by electron-beam coevaporation of Si and SiOx(x=1 or 2)

In this article, a simple and flexible electron-beam coevaporation (EBCE) technique has been reported of fabrication of the silicon nanocrystals (Si NCs) and their application to the nonvolatile memory. For EBCE, the Si and SiOx(x=1 or 2) were used as source materials. Transmission electron microscopy images and Raman spectra measurement verified the formation of the Si NCs. The average size and area density of the Si NCs can be adjusted by increasing the Si:O weight ratio in source material, which has a great impact on the crystalline volume fraction of the deposited film and on the charge storage characteristics of the Si NCs. A memory window as large as 6.6 V under +/- 8 V sweep voltage was observed for the metal-oxide-semiconductor capacitor structure with the embedded Si NCs.

Correlation between Er3+ emission and Si clusters in Erbium-doped a-SiOx : H films

Erbium-doped hydrogenated amorphous silicon suboxide films containing silicon clusters (a-SiOx:H) were prepared. The samples exhibited photoluminescence (PL) peaks at around 750nm and 1.54 mu m, which could be assigned to the electron-hole recombination in silicon clusters and the intra-4f transition in Er3+, respectively. We compared annealing behaviors of Si clusters and Er3+ emission and found that Si clusters emission depends strongly upon crystallinity of Si clusters, whereas Er3+ emission is not sensitive to whether it is Si nanocrystals (nc-Si) or amorphous Si (a-Si) clusters. The erbium-doped a-SiOx:H films containing either a-Si clusters or nc-Si have the same kind of Er3+ -emitting centers. Based on these results, it is concluded that a-Si clusters can play the same role on Er3+ excitation as nc-Si. (c) 2004 Elsevier B.V. All rights reserved.

Correlation between Er3+ emission and the microstructure of a-SiOx : H < Er > films

Photoluminescence (PL) from Er-implanted hydrogenated amorphous silicon suboxide (a-SiOX:H(x<2.0)) films was measured. Two luminescence bands with maxima at lambda congruent to 750 nm and lambda congruent to 1.54mum, ascribed to the a-SiOX:H intrinsic emission and Er3+ emission, were observed. Peak intensities of the two bands follow the same trend as a function of annealing temperature from 300 to 1000degreesC. Micro-Raman results indicate that the a-SiOX:H films are a mixture of two phases, an amorphous SiOX matrix and amorphous silicon (a-Si) domains embedded there in. FTIR spectra confirm that hydrogen effusion from a-SiOX:H films occurs during annealing. Hydrogen effusion leads to a reconstruction of the microstructure of a-Si domains, thus having a strong influence on Er3+ emission. Our study emphasizes the role of a-Si domains on Er3+ emission in a-SiOX:H films.

Microstructure of a-SiOx : H

A set of a-SiOx:H (0.52 < x < 1.58) films are fabricated by plasma-enhanced-chemical-vapor-deposition (PECVD) method at the substrate temperature of 250degreesC. The microstructure and local bonding configurations of the films are investigated in detail using micro-Raman scattering, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). It is found that the films are structural inhomogeneous, with five phases of Si, Si2O:H, SiO:H, Si2O3:H and SiO2 that coexist. The phase of Si is composed of nonhydrogenated amorphous silicon (a-Si) clusters that are spatially isolated. The average size of the clusters decreases with the increasing oxygen concentration x in the films. The results indicate that the structure of the present films can be described by a multi-shell model, which suggests that a-Si cluster is surrounded in turn by the subshells Of Si2O:H, SiO:H, Si2O3:H, and SiO2.

Influence of ambient atmosphere on the plasmon resonance absorption of Ag/SiOx(0 <= x <= 2) nanocomposite film

Nanocomposite films consisting of nanosized Ag particles embedded in partially oxidized amorphous Si-containing matrices were prepared by radio frequency magnetron co-sputtering deposition. We studied the influence of ambient atmosphere during the preparation and heat-treatment of Ag/SiOx (0 less than or equal to x less than or equal to 2) nanocompositefilm on its optical absorption properties. We found that the plasmon resonance absorption peak shifts to shorter wavelengths with the increasing oxygen content in the SiOx matrix. The analysis indicates that the potential barrier between Ag nanoparticles and SiOx matrix increases with the increasing x value, which will induce the surface resonance state to shift to higher energy. The electrons in the vicinity of the Fermi level of Ag nanoparticles must absorb more energy to be transferred to the surface resonance state with the increasing x value. It was also found that the plasmon resonance absorption peaks of the samples annealed in different ambient atmospheres are located at about the same position. This is because the oxidation surface layer is dense enough to prevent the oxygen from penetrating into the sample to oxidize the silicon in the inner layer.

Photoluminescence and microstructure of the Erbium-Doped hydrogenated amorphous SiOx(0 < x < 2)

The hydrogenated amorphous SiOx films (a-SiOx:H) with various oxygen contents have been prepared using plasma enhanced chemical vapor deposition technique. The films were implanted with erbium and annealed by rapid thermal annealing. An intense photoluminescence (PL) of Er at 1.54 mum has been observed at 77 K and at room temperature. The PL intensity depends strongly on both the oxygen content of the film and the rapid thermal annealing temperature and reaches its maximum if the ratio of O/Si in the film is approximately equal to 1.0 at 77 K and to 1.76 at room temperature. The microstructure of the film also has strong influences on the PL intensity. The PL intensity at 250 K is slightly more than a half of that at 15 K. It means that the temperature quenching effect of the PL intensity is very weak.

Photoluminescence of erbium-doped hydrogenated amorphous SiOx(0 < x < 2)

Hydrogenated amorphous SiOx films are fabricated via plasma enhanced chemical vapor deposition technique. After erbium implantation and rapid thermal annealing, photoluminescence (PL) are measured at 77 K and room temperature (RT), respectively. We observed the strong PL at 1.54 mu m at RT. The 1.54 mu m PL intensity changes with the variation of concentration of oxygen. The most intense PL at 77 K in a-SiOx:H (Er) corresponds to O/Si = 1.0 and at RT to O/Si = 1.76. Based on our results, we propose that Er ions contributed to PL come from O-rich region in the film. Er ions in Si-rich region have no relation with FL. Temperature dependence of the intensity of the 1.54 mu m line of the Er3+ transition displays a very weak temperature quenching in Er-doped hydrogenated amorphous Si. The PL intensity at 250 K is a little more one half of that at 15 K.

Microstructure of SiOx : H films prepared by plasma enhanced chemical vapor deposition

The micro-Raman spectroscopy and infrared (IR) spectroscopy have been performed for the study of the microstructure of amorphous hydrogenated oxidized silicon (alpha-SiOx,:H) films prepared by Plasma Enhanced Chemical Vapor Deposition technique. It is found that a-SiOx:H consists of two phases: an amorphous silicon-rich phase and an oxygen-rich phase mainly comprised of HSi-SiO2 and HSi-O-3. The Raman scattering; results exhibit that the frequency of TO-like mode of amorphous silicon red-shifts with decreasing size of silicon-rich region. This is related to the quantum confinement effects, similar to the nanocrystalline silicon.

Microstructure and photoluminescence of a-SiOx : H

Two strong photoluminescence (PL) bands in the spectral range of 550-900 nm have been observed at room temperature from a series of a-SiOx:H films fabricated by plasma-enhanced chemical vapor deposition (PECVD) technique. One is composed of a main band in the red-light region and a shoulder; the other is located at about 850 nm, only found after 1170 degrees C annealing in N-2 atmosphere. In conjunction with infrared (IR) and micro-Raman spectra, it is thought that the two PL bands are associated with a-Si clusters in the SiOx network and nanocrystalline silicon in SiO2, respectively.

Annealing behaviors of photoluminescence from SiOx : H

The strong photoluminescence (PL) of SiOx:H prepared by plasma enhanced chemical vapor deposition has been systematically studied in conjunction with infrared and micro-Raman spectra. We have found that each PL spectrum is comprised of two Gaussian components, a main band and a shoulder. The main band might originate from amorphous silicon clusters embedded in die SiOx network, and its redshift with annealing temperature is due to expansion of the silicon clusters. The shoulder remains at about 835 nm in spite of the annealing temperature and possibly comes from luminescent defect centers. The enhanced PL spectra after 1170 degrees C annealing are attributed to the quantum confinement effects of nanocrystalline silicon embedded in the SiO2 matrix. (C) 1998 American Institute of Physics.

A study of strong photoluminescence of SiOx : H films

We have examined photoluminescence (PL), IR absorption and Raman spectra of a series of hydrogenated amorphous silicon oxide (a-SiOx:H, (0 < x < 2)) films fabricated by plasma enhanced chemical vapor deposition (PECVD). Two strong luminescence bands were observed at room temperature, one is a broad envelope comprising a main peak around 670 nm and a shoulder at 835 nm, and the other, peaked around 850 nm; is found only after being annealed up to 1170 degrees C in N-2 environment. In conjunction with IR and Raman spectra, the origins of the two luminescent bands and their annealing behaviors are discussed on the basis of quantum confinement effects.