Embedded structure of silicon monoxide in SiO2 films

The structure of SiO_x (x = 1.94) films has been investigated using both X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The SiO_x films were deposited by vacuum evaporation. XPS spectra show that SiO_1.94 films are composed of silicon suboxides and the SiO₂ matrix. Silicon clusters appeared only negligibly in the films in the XPS spectra. Si₃O⁺ ion species were found in the TOF-SIMS spectra with strong intensity. These results reveal the structure of the films to be silicon monoxide embedded in SiO₂, and this structure most likely exists as a predominant form of Si₃O₄. The existence of Si-Si structures in the SiO₂ matrix will give rise to dense parts in loose glass networks.     

Intrinsic resistive switching and memory effects in silicon oxide

Resistive switching behaviors are described in silicon oxide (SiO _x ) systems employing vertical E/SiO _x /E (E denotes the electrode) structures. The switching is largely independent of the electrode material and attributed to the intrinsic properties of SiO _x . Based on the recent experimental observation (Yao et al. in Nano Lett. 10:4105, 2010) of a silicon filament embedded in the SiO _x matrix, we further discuss the switching mechanism in light of the measured electrical phenomena. The set voltages are largely SiO _x -thickness independent, consistent with the mechanistic picture of point switching in the silicon filament. The multi-state switching and shifts in the set voltages with respect to the reset voltages are consistent with an electrochemical redox process (Si ↔ SiO _y ) at the switching site.     

Study of the interface Si-nc/SiO2 by infrared spectroscopic ellipsometry and X-ray photoelectron spectroscopy

SiO_x films (1<x<2), 0.5 μm thick, have been elaborated by electron-gun evaporation. A thermal annealing of these films induced a phase separation leading to the formation of Si nanocrystals embedded in a SiO₂ matrix. These films have been studied by infrared spectroscopic ellipsometry and by X-ray photoelectron spectroscopy (XPS). The effective dielectric function of the thin films has been extracted in the 600–5000 cm⁻¹ range which allowed us to deduce the dielectric function of the matrix surrounding the Si-nc. A study of the Transverse Optical (TO) vibration mode has revealed the presence of SiO_x into the matrix. Before XPS measurements, the films have been etched in fluorhydric acid to remove the superficial SiO₂ layer formed during air exposure. The Si 2p core-level emission has been recorded. The decomposition of the Si 2p peak into contributions of the usual five tetrahedrons Si-(Si_4−nO_n) (n=0–4) has also revealed the presence of a SiO_x phase. Consistency between infra-red and XPS results is discussed.     

a-Si∶O∶H薄膜微结构及其高温退火行为研究

以微区Raman散射、X射线光电子能谱和红外吸收对等离子体增强化学气相沉积(PECVD)法制备的氢化非晶硅氧(a-Si∶O∶H)薄膜微结构及其退火行为进行了细致研究.结果表明a-Si∶O∶H薄膜具有明显的相分离结构,富Si相镶嵌于富O相之中,其中富Si相为非氢化四面体结构形式的非晶硅(a-Si),富O相为Si,O,H三种原子随机键合形成的SiO_x∶H(x≈1.35).经1150℃高温退火,薄膜中的H全部释出;SiO_x∶H(x≈1.35)介质在析出部分Si原子的同     

SiOx precipitate composition in Si,revisited: Discussion closed?

The composition SiO_x of oxide precipitates in Si has been discussed for the past thirty years with experimentally estimated x ‐values ranging between 1 and 2. It is shown that this spread of x ‐values can be explained by calculating the average composition taking into account temperature and anneal time dependent size and shape of the precipitates and the limitations and probing volumes of the various characterization techniques. Hereby it is assumed that the oxygen‐rich (SiO₂?) core of the precipitates is surrounded by a 2 nm thin SiO layer as revealed by recent electron energy loss spectroscopy analyses. For plate‐like precipitates thinner than and for octahedral precipitates smaller than 6 nm, x ≈ 1. For larger precipitates, the central part of the precipitate consists of SiO_x with x close to 2 and the precipitate has an average x between 1 and 1.3 for plate‐like and up to 1.9 for octahedral precipitates. The predicted x ‐values for different precipitate sizes and morphologies, are compared with published experimental data. SiO_x precipitate nucleation and initial growth should be simulated assuming x = 1 and Fourier transform infrared spectra of precipitates assuming a mixture of SiO₂ and amorphous Si. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ion-beam sputtering of quartz samples: Material properties observed in the mass spectra of secondary ions

Matrix effects are analyzed in the secondary ion mass spectra of quartz samples and SiO₂ and SiO _x films. The spectral relations between Si⁺, O⁺, and Si _n O _m ⁺ ions and the corresponding atomic fragments of the matrix are discussed. Previously revealed correlations between the mass spectrum and the structural features of SiO₂ and SiO _x are analyzed via the kinetic models of ion mixing.     

Study and applications of plasma-modified Si and porous Si surfaces

In this work we have studied the electrical, chemical and physical properties of CH_x/silicon and CH_x/porous silicon (PS). The hydrocarbon (CH_x) layer has been deposited by plasma of methane under argon atmosphere. Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) Spectroscopy and photoluminescence have been used to characterize the CH_x/p-Si, CH_x/PS interfaces and, electrolyte/(CH_x/p-Si) and CH_x/PS/p-Si structures. The results show that in the case of bare silicon, the CH_x layers act as a resistant film to HF electrolyte and can be used as a potential tool for ultra-low thickness for masking and patterning. The deposition of CH_x layer on PS shows that CH_x/PS/p-Si structure presents a rectifying behaviour and can be used for detecting low concentration of large variety of gases. In addition CH_x coated PS samples exhibit more intense luminescence than that observed from an uncoated PS surface where red luminescence is shown .In conclusion, the results clearly demonstrate the interest and applications of Si and PS electrodes coated with hydrocarbon groups.     

Inhomogeneous SiO<Subscript>x</Subscript>〈Fe〉 metal-dielectric films as a material for infrared thermal radiation detectors

A vacuum deposition method for producing SiO_x〈Fe〉 composite metal-dielectric films in which the metal concentration in the SiO_x dielectric matrix varies across thickness is described. The reflection and transmission of the films in the 2–12 μm IR spectral range are studied and their optical properties are simulated. In the temperature range 283–390 K, the temperature-sensitive properties of the SiO_x〈Fe〉 films with a phase volume ratio of 23% (Fe): 77% (SiO) is investigated. For these films, the temperature coefficient of resistance is found. The feasibility of these films as a sensitive layer in microbolometers is demonstrated.     

Substrate effect on mechanical relaxation of polystyrene in ultrathin films

Mechanical relaxation behavior in ultrathin polystyrene (PS) films supported on silicon oxide (SiO_x) and gold (Au) substrates has been studied by dynamic viscoelastic measurement. Based on the method, effects of free surface and substrate interface on the segmental dynamics were discussed. In the case of thin PS films with a thickness of approximately 200 nm, α_a-relaxation process corresponding to the segmental motion did not show any deviation from the bulk behavior. In contrast, for the films thinner than about 50 nm, the relaxation time distribution for the α_a-process became broader, probably due to a mobility gradient in the surface and interfacial regions. When we sandwiched an ultrathin PS film between SiO_x layers, another relaxation process, in addition to the original α_a-process, appeared at a higher temperature side that we assigned to the interfacial α_a-relaxation process. However, this was never seen for an ultrathin PS film between Au layers, implying that restriction from the substrate interface might be weak in this case.     

Electroluminescence of silicon nanocrystals in MOS structures

We have studied the structural, electrical and optical properties of MOS devices, where the dielectric layer consists of a substoichiometric SiO_x (x<2) thin film deposited by plasma-enhanced chemical vapor deposition. After deposition the samples were annealed at high temperature (>1000 °C) to induce the separation of the Si and the SiO₂ phases with the formation of Si nanocrystals embedded in the insulating matrix. We observed at room temperature a quite intense electroluminescence (EL) signal with a peak at ∼850 nm. The EL peak position is very similar to that observed in photoluminescence in the very same device, demonstrating that the observed EL is due to electron–hole recombination in the Si nanocrystals and not to defects. The effects of the Si concentration in the SiO_x layer and of the annealing temperature on the electrical and optical properties of these devices are also reported and discussed. In particular, it is shown that by increasing the Si content in the SiO_x layer the operating voltage of the device decreases and the total efficiency of emission increases. These data are reported and their implications discussed. Received: 31 August 2001 / Accepted: 3 September 2001 / Published online: 17 October 2001     

CORRELATION BETWEEN MORPHOLOGY AND MECHANICAL PROPERTIES OF DIFFERENT STYRENE/BUTADIENE TRIBLOCK COPOLYMERS: A SCANNING FORCE MICROSCOPY STUDY*

The morphology of different styrene/butadiene (SB) block copolymers with triblock architectures was investigated using tapping mode scanning force microscopy (SFM). Comparative analysis of the morphology of the samples at the polymer/substrate interface of solution-cast films and in bulk was performed. It was found that, besides the total phase volume ratio, the interfacial structure between the incompatible chains determines the phase morphology and mechanical properties of the investigated block copolymers. The asymmetric SBS triblock copolymer (φ_ps( 74 vol%) forms, as expected, a cylindrical morphology with hexagonally packed polybutadiene (PB) cylinders in the polystyrene (PS) matrix. Depending on the interfacial structure, block configuration, and the hard/soft phase ratio, other triblock copolymers (φ_ps( 74 vol% and 65 vol%) show lamellae and randomly distributed PS cylinders in a random styrene/butadiene copolymer S/B matrix, respectively.

     

Optical Properties and Structure of Electroluminescent SiOx:Tb Films

Using nondestructive optical methods (measurement of transmission spectra in the visible and IR regions and multiangular ellipsometry), we have studied the structural changes in SiO _x :Tb films subjected to high–temperature annealing in air, which are responsible for the appearance of electroluminescence in light–emitting structures based on them. It has been established that the appearance of green electroluminescence in such a film (upon annealing of the film in air at temperatures of 600–800°C) is due to the structural changes in its matrix, leading to partial disproportionation of the thermally deposited SiO _x :Tb film (as a result, the film represents a mixture of several phases – Si, SiO_x, and SiO₂). Films showing blue electroluminescence (annealing temperature 1000°C) are characterized by a higher content of oxygen, a better compactness, and a better macroscopic homogeneity in comparison with films showing green electroluminescence. It is also shown that the thermal cycling accompanying the annealing leads to the appearance of birefringence and scattering in SiO _x O:Tb films. It is anticipated that the annealing–stimulated structural changes taking place at both the micro– and the macrolevel should cause changes in the local surroundings of the luminescence center and in the conditions for heating the charge carriers exciting the luminescence centers.     

Preparation of PS/TiO2 as a white pigment for electrophoretic displays

PS (polystyrene)/TiO₂, TiO₂ coated onto PS by a hydrolysis reaction, was prepared as a white pigment for electronic paper (e-paper). Two key parameters, density and zetapotential, were precisely controlled for use as a white pigment. The density was manipulated by changing the mixture ratio of EtOH to H₂O, and the concentration of titanium tetrabutoxide (TBO) in the hydrolysis reaction. The modification of PS/TiO₂ with (3-aminopropyl)triethoxy silane (APTES) and acetic acid showed positive zetapotential originated from the mutual effects between an amino functional group in APTES, and a proton from acetic acid. The mutual effect was studied, and PS/TiO₂ with density of 1.6 g/cm² and zetapotential of 75 mV was prepared using the results.     

Defect reduction and surface passivation of SiO2/Si by heat treatment with high-pressure H2O vapor

Heat treatment with high-pressure H₂O vapor was applied to improve interface properties of SiO₂/Si and passivate the silicon surface. Heat treatment at 180–420 °C with high-pressure H₂O vapor changed SiO_x films, 150 nm thick formed at room temperature by thermal evaporation in vacuum, into SiO₂ films with a Si-O-Si bonding network similar to that of thermally grown SiO₂ films. Heat treatment at 130 °C with 2.8×10⁵ Pa H₂O for 3 h reduced the recombination velocity for the electron minority carriers from 405 cm/s (as-fabricated 150-nm-thick SiO_x/Si) to 5 cm/s. Field-effect passivation was demonstrated by an additional deposition of defective SiO_x films on the SiO₂ films formed by heat treatment at 340 °C with high-pressure H₂O vapor. The SiO_x deposition reduced the recombination velocity from 100 cm/s to 48 cm/s. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Absorption and emission of light in spark-processed silicon

Spark-processed Si (sp-Si) exhibits blue, green and red photoluminescence at around 385, 525 and 650 nm, depending on the wavelength of excitation. Its optical absorption spectrum reveals bands peaked approximately at 245, 277, 325 and 389 nm. The centers where absorption takes place were modeled as Si and silica clusters in an amorphous SiO_xN_y matrix using various embedding schemes. Geometry optimizations were applied prior to calculations of the absorption spectra of the clusters. The measured absorption spectrum of sp-Si and calculated absorption spectra were compared. Best agreement is achieved for Si particles embedded in amorphous SiO_xN_y matrix. The importance of the various embedding schemes is discussed and conclusions for the centers of emission are established.     

Optical and electronic polarizability investigation of Nd-doped soda-lime silicate glasses

This paper reports on different physical and optical properties of Nd³⁺-doped soda-lime silicate glass. The glasses containing Nd³⁺ in (65−x)SiO₂:25Na₂O:10CaO:xNd₂O₃ (where x=0.0-5.0 mol%) have been prepared by the melt-quenching method. In order to understand the role of Nd₂O₃ in these glasses the density, molar volume, refractive index and optical absorption were investigated. The results show that the density and molar volume of the glasses increase with an increase in Nd₂O₃ concentration and consequently generate more non-bridging oxygen (NBOs) into glass matrix. The optical absorption spectra were measured in the wavelength range from 300 to 700 nm and the optical band gaps were determined. It was found that the optical band gap decreases with an increase in Nd₂O₃ concentration. On the basis of the measured values of density and refractive index, the Nd³⁺ ion concentration in glasses, the polarizability of oxide ions and optical basicity were theoretically determined.     

Large-scale potential fluctuations caused by SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> compositional inhomogeneity

The short-range order in amorphous SiO _x (0 ≤ x ≤ 2) films has been studied by high-resolution X-ray photoelectron spectroscopy. Both the random bonding and random mixture models do not describe experimental photoelectron spectra of SiO _x (x ≤ 2). An intermediate model of the SiO _x structure has been proposed. The measured photoelectron spectra of the SiO _x (x ≤ 2) valence band indicate the presence of the silicon phase and silicon oxide.     

Electroluminescence properties of light emitting devices based on silicon nanocrystals

We have fabricated MOS devices where the dielectric layer consists of a substoichiometric SiO_x (x<2) thin film, annealed at 1100°C for 1 h to induce the separation of the Si and SiO₂ phases, with the formation of silicon nanocrystals (nc) embedded in the insulating matrix. We have studied the electroluminescence (EL) properties of such devices as a function of the current density and of the temperature. We have evaluated the excitation cross section of Si nc under electrical pumping at room temperature and at low temperature (12 K). Moreover, we have used the experimental EL intensities and decay times to evaluate the radiative rate as a function of the temperature.     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.