Preparation of composition-controlled silicon oxynitride films by sputtering; deposition mechanism,and optical and surface properties

Silicon oxynitride films have been grown on silicon by current-controlled reactive sputtering. The content of oxygen in the films could be well controlled by regulating the sputtering current under the reactive gas of Ar+ N₂ with an oxygen content of around 3%. The atomic ratio of oxygen to nitrogen in the silicon oxynitride film became larger with increasing sputtering current. It has been found that electron irradiation of the silicon substrate induces adsorption of oxygen and nitrogen. The degree of oxygen adsorption was about ten times larger than that of nitrogen. This phenomenon is a key mechanism in controlling the film composition. The adsorptive mechanism might be explained by the phenomenon of surface activation by the electron bombardment. Utilizing this technique, wettability by germanium of silicon oxynitride films could be controlled by varying their oxygen and nitrogen contents. A better wetting condition was obtained from films with large atomic ratio of nitrogen to oxygen in the silicon oxynitride film.     

First-principles studies of the oxygen adsorption on unreconstructed and reconstructed Ni(1 1 0) surfaces

First-principles calculations have been performed to investigate the adsorption of oxygen on unreconstructed and reconstructed Ni(1 1 0) surfaces. The energetics, structural, electronic and magnetic properties are given in detail. For oxygen adsorption on unreconstructed surface, (n×1)(n=2,3) substrate with oxygen atom on short-bridge site is found to be the most stable adsorption configuration. Whereas energetically most favorable adsorption phase of reconstructed surface is p(n×1) substrate with oxygen atom located at long-bridge site. Our calculations suggest that the surface reconstruction is induced by the oxygen adsorption. We also find there are redistributions of electronic structure and electron transfer from the substrate to adsorbate. Our calculations also indicate surface magnetic moment is enhanced on clean surfaces and oxygen atoms are magnetized weakly after oxygen adsorption. Interestingly, adsorption on unreconstructed surface does not change surface magnetic moment. However, adsorbate leads to reduction of surface magnetic moment in reconstructed system remarkably.     

The interference of an electron beam with the surface reaction between oxygen and germanium

Electron beam assisted adsorption and desorption of oxygen was studied by Auger electron spectroscopy (AES). Beam assisted adsorption was observed on clean as well as on oxidized surfaces. After an oxygen exposure of 1000 × 10^?7 Torr min and continuous irradiation with beam voltage of 1.5 kV and beam current density 2 microA mm^?2, the oxygen 510 eV signal amplitude from the point of beam impact was 2.5 times greater than the signal from the non-irradiated region. The Ge 89 eV signal showed a corresponding decrease. Enhanced adsorption occurred at beam energies as low as 16.5 eV. After irradiation, the oxidized surface was not carbon contaminated. Following an oxygen exposure of 30 min at 0.1 Torr and 550°C and subsequent additional beam assisted exposure of 1000 × 10^?7 Torr min, the maximum oxide thickness was about 18 Å. Beam assisted desorption did not occur from thin oxygen layers (0–510 eV signal strength less than 5 units, calculated oxide thickness about 6 Å), but occurred from thick oxides and stopped after the signal amplitude had decreased to 5 units. Based on these results, a model for the structure of the oxygen layer covering the Ge(111) surface is proposed. Mechanisms for adsorption and desorption are discussed. The implications of beam assisted adsorption and desorption on electron beam operated surface measurements (LEED, AES, ELS, APS etc.) are stressed.     

Enhancement of the electron-stimulated desorption from amorphous aluminum oxide films on silicon during an increase in the substrate temperature

The effect of high-temperature electron-stimulated desorption (ESD) from 20-nm-thick Al₂O₃ films deposited onto silicon wafers is studied. The ESD effect is found to be significantly enhanced upon heating. The films are found to decompose during ion beam irradiation of a heated substrate resulting in pure Al appearance. This process is accompanied by the formation of islands and almost pure silicon surface regions at a certain critical irradiation dose. Outside the irradiation zone, a 20-nm-thick Al₂O₃ film remains continuous even upon heating to 700°C and holding for 90 min. The effect of the primary electron beam energy on ESD from a 20-nm-thick Al₂O₃ film on silicon is investigated, and the parameters at which ESD takes place or absent are determined.     

Surface recombination velocity in a silicon optical waveguide

Measurements of the varying infrared absorption by free carriers in a silicon waveguide during intermittent electron bombardment are used to study the surface recombination velocitys. The same values for s are obtained for heat-treated and untreated samples, which supports the theory that electron beam irradiation in itself has a dehydrating effect. Other experiments show thats is not dependent on the energy of the impinging electrons in the range 16–23 keV. Finally, the temperature dependence ofs in gold-doped silicon is estimated. Ifs is written in the forms=s ₀(293/T)^x,x is found to be 2.1±0.2 in the temperature interval 261K≦T≦309K.     

Kinetics of electron-stimulated oxygen adsorption on the lead surface

Auger electron spectroscopy has been used to study the kinetics of oxygen adsorption on lead for two cases, i.e., during continuous electron irradiation (0–1000 eV) and without it, depending on exposure to oxygen at a partial pressure of 10^?6 Torr and room temperature. The maximum exposure to oxygen is 5000 L. Lead exposure to oxygen of several hundred Langmuirs with simultaneous irradiation with low-energy electrons shifts Auger lead peaks by 1 eV toward lower energies, which is explained by electron-stimulated adsorption (ESA). It has been shown that ESA is observed only at electron energies below 300 eV; at higher energies, electron-stimulated desorption of oxygen dominates.     

An infra-red study of defects produced in n-type silicon by electron irradiation at low temperatures

The infra-red local mode absorption produced by irradiation of n-type silicon by 2 MeV electrons at temperatures in the range 100–140°K has been investigated. A new band at 884 cm^-1 has been observed and interpreted as due to a vacancy— oxygen complex (A-centre) with a trapped electron.     

Untersuchung von Raumladungsschichten an Zinkoxid-Oberflächen mit Hilfe der Elektroreflexion

Using the electroreflectance method space charge layers on crystals of different conductivities have been identified. The space charge layers were formed by adsorption of oxygen or atomic hydrogen. The limit of sensitivity required the irradiation with 5×10¹³ photons/cm²×sec of band gap energy. After exposure to atomic hydrogen all samples showed accumulation layers. With a partial pressure of oxygen above 350 mm Hg crystals of high conductivity (σ=47 ohm^?1 cm^?1) exhibit depletion layers, which change into accumulation layers, if the partial pressure is reduced below the limit. Crystals of a lower conductivity (σ=10^?3–10^?1 ohm^?1 cm^?1) show accumulation layers up to the highest applied oxygen pressure of 760 mm Hg. The phenomena are attributed to a dynamical equilibrium between adsorption and photo-desorption of oxygen. This equilibrium depends on oxygen pressure and free carrier concentration. By comparing a calculated curve with the experimental results the value of 3.31 ev is obtained for the energy gap, light polarized perpendicular to thec-acis.     

Surface disorder in c-Si induced by swift heavy ions

The disorders induced in crystalline silicon (c-Si) through the process of electronic energy loss in the swift heavy ion irradiation were investigated. A number of silicon <1 0 0> samples were irradiated with 65 MeV oxygen ions at different fluences, 1×10¹³ to 1.5×10¹⁴ ions/cm², and characterized by the Raman spectroscopy, the optical reflectivity, the X-ray reflectivity, the atomic force microscopy (AFM) and the X-ray diffraction (XRD) techniques. The intensity, redshift, phonon coherence length and asymmetric broadening associated with the Raman peaks reveal that stressed and disordered lattice zones are produced in the surface region of the irradiated silicon. The average crystallite size, obtained by analyzing Raman spectrum with the phonon confinement model, was very large in the virgin silicon but decreased to<100 nm dimension in the ion irradiated silicon. The results of the X-ray reflectivity, AFM and optical reflectivity of 200–700 nm radiation indicate that the roughness of the silicon surface has enhanced substantially after ion irradiation. The diffusion of oxygen in silicon surface during ion irradiation is evident from the oscillation in the X-ray reflectivity spectrum and the sharp decrease in the reflectivity of 200–400 nm radiation. The rise in temperature, estimated from the heat spike model, was high enough to melt the local silicon surface. The results of XRD indicate that lattice defects have been induced and a new plane <2 1 1> has been formed in the silicon <1 0 0>after ion irradiation. The results of the present study show that the energy deposited in crystalline silicon through the process of electronic energy loss ～0.944 keV/nm per ion is sufficient to induce disorders of appreciable magnitude in the silicon surface even at a fluence of ～10¹³ ions/cm².     

Defect sites in thin films of germanium dioxide irradiated with silicon ions

Optical transmission spectra of GeO₂ films irradiated with silicon ions and subjected to postimplantation annealing in the regime of silicon nanocrystal formation are analyzed. It is shown that point defects form in the films after irradiation with doses D ～ 10²⁰ m^?2: germanium electron centers, neutral oxygen vacancies, and Ge²⁺ centers, which have been annealed at a temperature of 1000°C for an hour. At D ≥ 1 × 10²¹ m^?2, more complex defects arise in the films, which are only partially annealed under the same conditions.     

A proposed experiment to measure surface roughness in Si/SiO2 system

The adsorption of oxygen on clean cleaved (111) silicon surfaces has been investigated by high resolution electron spectroscopy (HRES), Auger electron spectroscopy (AES) and ellipsometry. Localized vibrations ($\text{h}\text{?}\text{ω = 94}$, 130 and 175 meV) which are related to the binding state band of oxygen are identified with HRES. AES measures the concentration of adsorbed atoms basically independent of their binding state while ellipsometry refers additionally to the optical properties of the adsorbed layer. The same adsorption kinetics was found with the three methods. Oxygen therefore adsorbs in a single likely molecular state. The sticking coefficient S increases exponentially with the surface step concentration. S is also enhanced by the presence of nude ion gauges. Depending on these parameters sticking coefficients between 2 × 10^?4 and 10^?1 have been obtained. This result might contribute to an explanation of the large differences in earlier works.     

Vibrational excitations of p(2×2) oxygen and c(2×2) hydrogen on Pd(100)

The p(2×2) oxygen and c(2×2) hydrogen structures on Pd(100) have been investigated by angle-resolved high-resolution electron energy loss spectroscopy. Dipole excited vibrational modes are observed at 44 and 64 meV for the oxygen and hydrogen structures respectively and are interpreted to correspond to atomic adsorption in the hollow site.     

Influence of irradiation on the thermal decomposition of lithium perchlorate

Abstract

Infrared absorption measurements were made before and after 90 °K electron irradiations of silicon samples which contained either dispersed oxygen, carbon, or carbon plus oxygen. Irradiation-produced absorption bands associated with two distinctly different defects are observed depending on the oxygen and carbon content of the silicon. One center is the well-known vacancy-oxygen A-center defect (836-cm^?1 band) and is formed on irradiation in oxygen-containing silicon with a magnitude which is independent of the carbon content. Measurements have correlated the formation of one A-center with the loss of one interstitial oxygen atom, thereby indicating that A-center formation occurs by vacancy trapping at interstitial oxygen atoms. A second center (922-and 932-cm^?1 bands) is formed only in silicon crystals which contain both oxygen and carbon. The results indicate that this center is formed by the trapping of a silicon interstitial at a carbon-oxygen complex.     

Effect of electron irradiation on the oxidation of indium

The oxidation kinetics of indium is studied for two cases, namely, during continuous electron irradiation (E _p = 1800 eV) and without electron irradiation, as a function of the time of exposure to an oxygen medium at a partial oxygen pressure of 10⁻⁴ Pa and room temperature. The initial oxygen exposure was 50 L. The kinetic curves recorded upon continuous electron irradiation have two inflection points, and they can be attributed to the following three states of oxidation: physical adsorption, chemisorption with the formation of a nonstoichiometric oxide layer, and the growth of a homogeneous oxide layer. Only the first inflection point is observed during oxidation without electron irradiation, and further exposure does not lead to the second inflection point within the experimental time.     

Hydrogen chemisorption on silicon (100) 2 × 1

Changes in the valence band density of states (DOS) of a (100) silicon surface that accompany he chemisorption of atomic hydrogen onto that surface are deduced from a study of the changes in the L_2,3VV Auger lineshape. Complementary changes in the conduction band DOS are inferred from changes in L_2,3VV-core-level characteristic loss spectra (CLS). The chemisorbed hydrogen layer is identified as the dihydride phase from low energy electron diffraction measurements. Upon hydrogen adsorption the DOS at the top of the valence band decreases and new energy levels associated with the Si-H bonds appear lower in the band. Assuming that the Auger signal from the hydrogen covered sample consists of a superposition of a signal from silicon atoms bonded to hydrogen in the dihydride layer and an elemental-Si signal from the substrate, a N(E) difference spectrum with features due only to the dihydride is obtained by subtracting the background corrected, loss deconvoluted L_2,3VV signal for a clean (100)Si surface rom the corresponding signal for the hydrogen covered surface. Comparisons of the energy position of the major peak in this difference spectrum with that of the main peak in a gas phase silane Si-L_2,3VV spectrum, and of the corresponding Auger energy calculated empirically, indicate a hole—hole interaction energy of ~8 eV for the two-hole final state in the gaseous system and zero for the dihydride surface system. Hydrogen induced changes in the conduction band DOS are less apparent than those of the valence band DOS with only the possibility of a decrease in the DOS at the bottom of the conduction band being inferred from the CLS measurements. Electron stimulated desorption of hydrogen from the dihydride layer is adduced from changes in the Auger lineshape under electron beam irradiation of the surface. Hydrogen induced changes in the near-elastic electron energy loss spectra (ELS) are also reported and compared with previously published ELS results.     

Structures near the L2,3 core edges of clean and: Oxygen covered Si(111) studied with low-energy electrons

The L_2,3 core excitation spectra of clean and oxygen covered surfaces of Si(111), measured in low-energy electron energy loss Spectroscopy reproduce previous results obtained with highenergy electrons or synchrotron radiation. It is inferred that among the different transition channels, the matrix elements for the dipole term dominate. Spectra on oxidized surfaces indicate that oxygen adsorption on Si(111) induces the formation of SiO₄ structural units.     

Chemisorption,surface structural chemistry,and electron impact properties of carbon monoxide on rhodium (110)

The adsorption, desorption, surface structural chemistry, and electron impact properties of CO on Rh(110) have been studied by LEED, Auger spectroscopy, thermal desorption, and surface potential measurements. At 300 K, CO adsorbs into a single chemisorbed state whose desorption energy (E_d) is ~130kJmol^-1. The initial sticking probability is unity, and at saturation coverage a (2 × 1)plgl ordered phase reaches its maximum degree of perfection, thus demonstrating that this CO structure is common to the (110) faces of all the cubic platinum group metals. The saturated adlayer corresponds to θ = 1 and shows a surface potential of Δ? = +0.97 V. Under electron impact, desorption and dissociation of CO occur with about equal probability, the relevant cross sections being ~10^-22 m² in each case. Slow thermal dissociation of CO occurs at high temperature and pressure, leaving a deposit of C and O atoms on the surface. The thermal, electron impact, and Δ? properties of Rh(110)CO resemble those of Ni(110)CO rather closely, and are very different from those of Pt(110)CO. Surface carbon is shown to inhibit CO chemisorption, whereas surface oxygen appears to lead to the formation of a new more tightly bound form of CO with a considerably enhanced desorption energy (E_d ~ 183 kJmol^-1). Similar oxygen-induced high temperature CO states have been reported recently on Co(0001) and Ru(101&#x0304;1).     

Coadsorption of oxygen and sodium on Ru(001)

The interaction of oxygen with sodium predosed Ru(001) is studied by means of thermal desorption, Auger and electron loss spectroscopy and work function measurements. The initial sticking coefficient of oxygen is found to increase from 0.45 for bare Ru(001) to 1 for Ru(001) with a 0.35 monolayer sodium coverage. The adsorption capacity of the sodium predosed Ru(001) surface towards oxygen is enhanced from θ_O = 0.5 for clean Ru(001) to θ_O = 1.4 for Ru(001) with a 0.7 monolayer sodium coverage. The work function, electron loss changes and thermal desorption data give evidence that as long as θ_Na is less than 0.25, the oxygen chemisorption phase is characterized mainly by oxygen-Ru bonds and by the absence of strong sodium-oxygen interactions. At high sodium coverages (θ_Na > 0.35), the experimental data indicate the formation of a Na-O compound in the second adsorption layer at high oxygen exposures. When Ru(100) is predosed with sodium (θ_Na ? 0.25), this leads to complete suppression of oxygen penetration into the bulk during heating, the latter process being observed for the oxygen-Ru(001) system.     

Defects in electron-irradiated 3C-SiC epilayers observed by positron annihilation

Positron annihilation has been used to study defects induced by 1 MeV electron irradiation in cubic silicon carbide (3C-SiC) epitaxially grown on Si substrates by chemical vapor deposition. Narrowing of the Doppler-broadened energy spectrum of annihilation gamma-rays by the electron irradiation was observed in the fluence range above 5 × 10¹⁶ e/cm². The electron fluence dependence of the narrowing is accounted for by the introduction of monovacancies and divacancies in 3C-SiC by the irradiation.     

Thermoelectrics from silicon nanoparticles: the influence of native oxide

Thermoelectric materials were synthesized by current-assisted sintering of doped silicon nanoparticles produced in a microwave-plasma reactor. Due to their affinity to oxygen, the nanoparticles start to oxidize when handled in air and even a thin surface layer of native silicon oxide leads to a significant increase in the oxide volume ratio. This results in a considerable incorporation of oxygen into the sintered pellets, thus affecting the thermoelectric performance. To investigate the necessity of inert handling of the raw materials, the thermoelectric transport properties of sintered nanocrystalline silicon samples were characterized with respect to their oxygen content. An innovative method allowing a quantitative silicon oxide analysis by means of electron microscopy was applied: the contrast between areas of high and low electrical conductivity was attributed to the silicon matrix and silicon oxide precipitates, respectively. Thermoelectric characterization revealed that both, electron mobility and thermal conductivity decrease with increasing silicon oxide content. A maximum figure of merit with zT = 0.45 at 950 °C was achieved for samples with a silicon oxide mass fraction of 9.5 and 21.4% while the sample with more than 25% of oxygen clearly indicates a negative impact of the oxygen on the electron mobility.