XRR and GISAXS study of silicon oxynitride films

Thin films of silicon oxynitride have largely replaced pure silicon oxide films as gate and tunnel oxide films in modern technology due to their superior properties in terms of efficiency as boron barrier, resistance to electrical stress and high dielectric strength. A single chamber system for plasma enhanced chemical vapor deposition was employed to deposit different films of SiO_xN_yH_z with 0.85 < x < 1.91. All films were previously characterized by Rutherford back-scattering and infrared spectroscopy to determine the stoichiometry and the presence of various bonding configurations of constituent atoms. We used X-ray reflectivity to determine the electron density profile across the depth, and we showed that the top layer is densified. Moreover, grazing incidence small-angle X-ray scattering was used to study inhomogeneities (clustering) in the films, and it is shown that plate-like inhomogeneities exist in the top and sphere-like particles at the bottom part of the film. Their shape and size depend on the stoichiometry of the films.     

Effect of thermal annealing on the formation of silicon nanoclusters in SiOX films grown by PLD

Silicon nanoclusters formation in pulsed laser deposited (PLD) silicon suboxide (SiO_X) films by thermal annealing is reported. The SiO_X films are prepared by ablation of silicon target at different oxygen partial pressures. The different deposition conditions are employed to study the effect of oxygen concentration on the size of the nanoclusters. Post deposition thermal annealing of the films leads to the phase separation in silicon suboxide films. Fourier transform infrared spectroscopy, micro-Raman spectroscopy and UV-vis absorption spectroscopy studies were carried out to characterize the formation of silicon nanoclusters in SiO_X films.     

X-ray reflectivity and photoelectron spectroscopy of superlattices with silicon nanocrystals

The structural properties and features of the chemical composition of SiO _x N _y /SiO₂, SiO _x N _y /Si₃N₄, and SiN _x /Si₃N₄ multilayer thin films with ultrathin (1–1.5 nm) barrier SiO₂ or Si₃N₄ layers are studied. The films have been prepared by plasma chemical vapor deposition and have been annealed at a temperature of 1150°С for the formation of silicon nanocrystals in the SiO _x N _y or SiN _x silicon-rich layers with a nominal thickness of 5 nm. The period of superlattices in the studied samples has been estimated by X-ray reflectivity. The phase composition of superlattices has been studied by X-ray electron spectroscopy using the decomposition of photoelectron spectra of the Si 2p, N 1s, and O 1s levels into components corresponding to different charge states of atoms.     

Raman and infrared spectra of doped La8+xSr2−y(SiO4)6O2+δ compounds compared to the ab initio‐obtained spectroscopic characteristics of fully stoichiometric La8Sr2(SiO4)6O2

Vibrational spectroscopy data were used to gain insight into the possible locations of extra oxygen ions introduced into La_8+xSr_2−y(SiO₄)₆O_2+δ compounds to raise their ionic conductivity. Perturbations observed in the Raman and infrared spectra of these compounds with increasing δ were explained by using the ab initio calculation results for the fully stoichiometric (x = y = δ = 0) lattice. This allowed the inference that the extra oxygen ions are incorporated into La O tunnel‐like fragments inherent in the studied structures. Copyright © 2010 John Wiley & Sons, Ltd.     

Formation of silicon oxide nanowires directly from Au/Si and Pd–Au/Si substrates

Amorphous silicon oxide (SiO_x) nanowires were directly grown by thermal processing of Si substrates. Au and Pd–Au thin films with thicknesses of 3 nm deposited on Si (0 0 1) substrates were used as catalysts for the growth of nanowires. High-yield synthesis of SiO_x nanowires was achieved by a simple heating process (1000–1150 °C) in an Ar ambient atmosphere without introducing any additional Si source materials. The as-synthesized products were characterized by field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy measurements. The SiO_x nanowires with lengths of a few and tens of micrometers had an amorphous crystal structure. The solid–liquid–solid model of nanowire formation was shown to be valid.     

Infrared and auger spectra of dysprosium silicate films

Dysprosium silicate films, Dy _x Si _y O _z , have been investigated using infrared (IR) and Auger spectroscopy. The films have been formed by oxidizing dysprosium metal films on 5.2-nm-thick silicon dioxide films at a temperature of 600°C. It is shown that the composition of the Dy _x Si _y O _z dysprosium silicate films is close to that of dysprosium pyrosilicate, Dy₂Si₂O₇, and irregular in thickness. On going from the film outer surface to the silicon substrate, the amount of dysprosium decreases and that of silicon bound to oxygen increases. Silicon dioxide, SiO₂, predominates in the layer composition near the silicon substrate. The dielectric leakage current density in the accumulation mode is one order of magnitude lower in the Dy _x Si _y O _z films than in the SiO₂ films of the same equivalent thickness due to the larger physical thickness of the former.     

FTIR and spectroscopic ellipsometry investigations of the electron beam evaporated silicon oxynitride thin films

FTIR and variable angle spectroscopic ellipsometer in conjunction with computer simulation were employed to investigate the electron beam evaporated SiO_xN_y thin films. FTIR showed a large absorption band located between 600 and 1250 cm⁻¹, which indicates that Si-O and Si-N bands are overlap in SiO_xN_y films. A three layers model was used to fit the calculated data to the experimental ellipsometric spectra. The main layer was described by Cauchy model while the interface layer and the surface layer were described using Tauc-Lorenz oscillator and Bruggeman effective medium approximation, respectively. The thickness, the refractive index and the extinction coefficient were accurately determined. The refractive index at 630 nm was found to increase from 1.74 to 1.85 with increasing the film thickness from 191.6 to 502.2 nm. The absorption coefficient was calculated from the obtained extinction coefficient values and it has been used to calculate the Tauc and Urbach energies.     

Chemical and phase compositions of silicon oxide films with nanocrystals prepared by carbon ion implantation

The chemical and phase compositions of silicon oxide films with self-assembled nanoclusters prepared by ion implantation of carbon into SiO _x (x < 2) suboxide films with subsequent annealing in a nitrogen atmosphere have been investigated using X-ray photoelectron spectroscopy in combination with depth profiling by ion sputtering. It has been found that the relative concentration of oxygen in the maximum of the distribution of implanted carbon atoms is decreased, whereas the relative concentration of silicon remains almost identical over the depth in the layer containing the implanted carbon. The in-depth distributions of carbon and silicon in different chemical states have been determined. In the regions adjacent to the layer with a maximum carbon content, the annealing results in the formation of silicon oxide layers, which are close in composition to SiO₂ and contain silicon nanocrystals, whereas the implanted layer, in addition to the SiO₂ phase, contains silicon oxide species Si²⁺ and Si³⁺ with stoichiometric formulas SiO and Si₂O₃, respectively. The film contains carbon in the form of SiC and elemental carbon phases. The lower limit of the average size of silicon nanoclusters has been estimated as ∼2 nm. The photoluminescence spectra of the films have been interpreted using the obtained results.     

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.     

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.     

Effects of post-thermal annealing temperature on the optical and structural properties of gold particles on silicon suboxide films

In this work, silicon suboxide (SiO_x) thin films were deposited using a RF magnetron sputtering system. A thin layer of gold (Au) with a thickness of about 10 nm was sputtered onto the surface of the deposited SiO_x films prior to the thermal annealing process at 400 °C, 600 °C, 800 °C and 1000 °C. The optical and structural properties of the samples were studied using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and optical transmission and reflection spectroscopy. SEM analyses demonstrated that the samples annealed at different temperatures produced different Au particle sizes and shapes. SiO_x nanowires were found in the sample annealed at 1000 °C. Au particles induce the crystallinity of SiO_x thin films in the post-thermal annealing process at different temperatures. These annealed samples produced silicon nanocrystallites with sizes of less than 4 nm, and the Au nanocrystallite sizes were in the range of 7-23 nm. With increased annealing temperature, the bond angle of the Si-O bond increased and the optical energy gap of the thin films decreased. The appearance of broad surface plasmon resonance absorption peaks in the region of 590-740 nm was observed due to the inclusion of Au particles in the samples. The results show that the position and intensity of the surface plasmon resonance peaks can be greatly influenced by the size, shape and distribution of Au particles.     

Activation energy of hydrogen desorption from high-performance titanium oxide carrier-selective contacts with silicon oxide interlayers

The impact of hydrogen desorption on the electrical properties of TiO_x on crystalline silicon (c-Si) with SiO_y interlayers is studied for the development of high-performance TiO_x carrier-selective contacts. Compared with the TiO_x/c-Si heterocontacts, a lower surface recombination velocity of 9.6 cm/s and lower contact resistivity of 7.1 mΩ cm² are obtained by using SiO_y interlayers formed by mixture (often called SC2). The hydrogen desorption peaks arising from silicon dihydride (α1) and silicon monohydride (α2) on the c-Si surface of the as-deposited samples are observed. The α1 peak pressure of as-deposited heterocontacts with SiO_x interlayers is lower than that of heterocontacts without a SiO_y interlayer. Furthermore, the hydrogen desorption energies are found to be 1.76 and 2.13 eV for the TiO_x/c-Si and TiO_x/SC2-SiO_y/c-Si heterocontacts, respectively. Therefore, the excellent passivation of the TiO_x/SC2-SiO_y/c-Si heterocontacts is ascribed to the relatively high rupture energy of bonding between Si and H atoms.     

Optimization of plasma-deposited silicon oxinitride films for optical channel waveguides

In view of applications of SiO_xN_y thin films in MOEMS technology, a study of the optomechanical characteristics of the PECVD deposited material are investigated. To optimize the quality of SiO_xN_y layers we establish the relationship between the chemical properties, optical performances, micromechanical stress, and growth parameters of deposited films. To use the SiO_xN_y thin film for the core layer of a strip-loaded waveguide, we propose preparation conditions of SiO_xN_y that offer a low-loss optical waveguide with well-controlled refractive index, based on a low-internal stress multilayer structure.     

Pulsed laser deposition of praseodymium oxide films on silicon(100)

In this study, pulsed laser deposition (PLD) was used to deposit thin films of high-k dielectric praseodymium oxide on silicon(100). Photoluminescence spectroscopy (PL) shows the possibility of activating crystal defects in the Si substrate during the PLD process. Capacitance-Voltage (C–V) measurements yield an average dielectric constant of k=33 for Pr_xO_y films of different thicknesses. The leakage current is orders of magnitude lower than for SiO₂. PACS 77.55; 81.15.Fg     

Vibrational Assignment of 2-Benzoyl Pyridine and its 18O Labelled Isomer

Abstract

Vibrational spectra of 2-benzoyl pyridine and 2-benzoyl pyridine-¹⁸O have been recorded in the solid and molten state in the infrared (4000–100 cm^?1) and in the Raman (4000–50 cm^?1). Polarized Raman spectra in the molten state have also been measured. The assignment of the vibrational bands is performed using the group vibrational concept, isotopic shifts and polarization features of the normal modes.     

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.     

Photoluminescence and optical absorption properties of silicon quantum dots embedded in Si-rich silicon nitride matrices

Silicon nitride (SiN_x) films were prepared with a gas mixture of SiH₄ and NH₃ on Si wafers using the plasma-enhanced chemical vapor deposition (PECVD) method. High-resolution transmission electron microscopy and infrared absorption have been used to reveal the existence of the Si quantum dots (Si QDs) and to determine the chemical composition of the silicon nitride layers. The optical properties of these structures were studied by photoluminescence (PL) spectroscopy and indicate that emission mechanisms are dominated by confined excitons within Si QDs. The peak position of PL could be controlled in the wavelength range from 1.5 to 2.2 eV by adjusting the flow rates of ammonia and silane gases. Absorbance spectra obtained in the transmission mode reveal optical absorption from Si QDs, which is in good correlation with PL properties. These results have implications for future nanomaterial deposition controlling and device applications.     

Correlation between structure and photoluminescence in amorphous hydrogenated silicon nitride alloys

As-deposited a-SiN_x:H (0.1<x<0.9) thin films prepared by evaporation of silicon under a flow of nitrogen and hydrogen ions exhibit visible photoluminescence at room temperature without any posttreatment. The nitrogen concentration was determined by X-ray photoemission spectroscopy. The structural characterization was performed with Fourier transform infrared absorption spectroscopy. The optical gap was obtained from transmission measurements in the ultraviolet–visible–near infrared range. These studies were correlated to the evolution of the photoluminescence properties.     

Fabrication of polycrystalline silicon films by Al‐induced crystallization of silicon‐rich oxide films

Polycrystalline silicon (poly‐Si) films were fabricated by aluminum (Al)‐induced crystallization of Si‐rich oxide (SiO_x) films. The fabrication was achieved by thermal annealing of SiO_x /Al bilayers below the eutectic temperature of the Al–Si alloy. The poly‐Si film resulting from SiO_1.45 exhibited good crystallinity with highly preferential (111) orientation, as deduced from Raman scattering, X‐ray diffraction, and transmission electron microscopy measurements. The poly‐Si film is probably formed by the Al‐induced layer exchange mechanism, which is mediated by Al oxide.     

Far Infrared and Raman Spectra of Some Crystalline Iodomercurate Complexes

Abstract

Vibrational spectra of crystalline powders of [Nien₂] [HgI₃]₂ and [Men₂] [HgI₄] (where en = ethylene-diamine chelated to M = Ni(II), Pd(II) or Pt(II)) have been measured at room and liquid-nitrogen temperatures. The bands observed in the low frequency region 200–10 cm^?1 are interpreted in terms of mainly internal vibrations of the anions and external lattice modes. Raman and far infrared spectra are compared in order to make structural deductions. In comparison with present knowledge of the stereochemistry and vibrational spectroscopy of other iodomercurates, the triiodo-mercurate salt seems to contain nearly planar trigonal anions, while the tetraiodomercurates contain discrete tetrahedra. Probable site symmetries of the anions which may explain the spectra are discussed.