A new method for determining relaxation energies by means of aes and xps and its application to silicon compounds

A new method is presented for the determination of the absolute dynamic relaxation energy R_D from experimental Auger parameters, the static dielectric constant and the plasmon energy of the solids. The relaxation energies of the Si 1s and 2p core levels in Si, SiC, SiO₂, Si₃N₄ and Na₂SiF₆ are investigated by comparing the experimental values with theoretical results from a semiempirical dielectric theory. Both the experimental and theoretical results are valid only for the least-bound Si 2p state. The calculated relaxation shifts ΔR_D^ea(1s) and ΔR_D^ea(2p) are in reasonable agreement with the experimental values, and describe the extraatomic polarization effect well also for a deep level.     

Structure of self-implanted silicon annealed under enhanced hydrostatic pressure

Implantation of any ions at a sufficiently high dose and energy (E) into single-crystalline Si leads to the creation of amorphous Si (aSi), with damages peaking near the projected range (R _p) of implanted species. Enhanced hydrostatic pressure (HP) at a high temperature (HT) influences the recrystallization of aSi. The structure of self-implanted Czochralski silicon (Si⁺ dose, D=2×10¹⁶ cm^?2, E=150 keV, R _p=0.22 μm) processed for 5 h at 1400 or 1520 K under HPs up to 1.45 GPa was investigated by X-ray, secondary ion mass spectrometry and photoluminescence methods. The implantation of Si produces vacancies (V) and self-interstitials (Si_i). Vacancies and Si_is form complex defects at HT–HP, also with contaminants (e.g. oxygen, always present in Czochralski silicon). The mobility and recombination of V and Si_i as well as the kinetics of recrystallization are affected by HP, thus processing at HT–HP affects the recovery of aSi.     

Extra-atomic electronic cross-relaxation energies in KL2,3L2,3 Auger transitions in small sodium clusters from SCF-Xα-SW calculations

The self-consistent-field-Xα-scattered-wave method is used to calculate extra-atomic electronic cross-relaxation energies R_C^ea involved in KL_2,3L_2,3 Auger transitions in a series of small sodium clusters. R_C^ea is shown to increase with increasing dimension of the cluster. The R_C^ea value for Na₁₅ already closely approaches the metallic value. It is felt that the present calculational method will also be useful in determining relaxation energies in chemisorption systems.     

Reconfigurations and diffusion of trivacancy in silicon

Disappearance of the divacancy (V₂) and trivacancy (V₃) complexes upon isochronal and isothermal annealing of electron irradiated Si:O crystals has been studied by means of deep level transient spectroscopy. The annealing studies have shown that the V₂ and V₃ defects are mobile in Si at T>200 °C and in oxygen-rich material are trapped by interstitial oxygen atoms so resulting in the appearance of V₂O and V₃O defects. The activation energies for diffusion of the V₂ and V₃ centers have been determined. Density functional modeling calculations have been carried out to investigate the migration and reorientation mechanisms of V₃ in large silicon supercells. It is proposed that these comprise a sequence of transformations between V₃(D₃) and V₃(C_2v) configurations.     

The structure of theL 2,3 VV-auger line of silicon and silicon compounds

TheL _2,3 VV Auger transitions of Si, SiO₂, and SiC have been measured and compared with the self-fold electron density of states. The data indicate that Auger matrix effects must be included to explain the structure of the Auger lines. A comparison with soft X-ray measurements of Wiech shows, that the measured Auger line shape is nearly identical with the self-foldK _β emission band. The selection rules for X-ray emission lead then to the conclusion that mostlyp-like valence electrons are involved in the Auger transition. This result indicates the relative importance ofs andp states in Auger transitions which is in accordance with theoretical calculations of Feibelman et al.     

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si₃N₄ (Si⁴⁺) but also in the intermediate nitridation states with one (Si¹⁺) or three (Si³⁺) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si¹⁺, Si³⁺, and Si⁴⁺ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si⁴⁺ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si₃N₄ by molecular beam epitaxy (MBE).     

Interfacial auger transitions in oxidised sodium and magnesium

A study of the oxidation of sodium and magnesium under precisely controlled U.H.V. conditions using Auger electron spectroscopy has revealed the presence of Auger transitions which may be interpreted as arising from the interface between the oxide and the underlying metal. These Auger peaks have been assigned transitions of the type: M¹(L_2,3) M(V) O¹(L) where M¹ and O¹ are ionic levels present in the oxide and one of the final state holes M(V) is in the conduction band. The experimentally observed Auger energies agree well with those calculated for the proposed transitions. It is expected that transitions of this type might occur in other metal—oxide systems.     

Magnetic moment relaxation of a shallow acceptor center in heavily doped silicon

Results of studying the temperature dependence of the residual polarization of negative muons in crystalline silicon with germanium (9×10 ¹⁹ cm ^?3 ) and boron (4.1×10 ¹⁸ , 1.34×10 ¹⁹ , and 4.9×10 ¹⁹ cm ^?3 ) impurities are presented. It is found that, similarly to n-and p-type silicon samples with impurity concentrations up to ～10 ¹⁷ cm ^?3 , the relaxation rate ν of the magnetic moment of a _μ Al acceptor in silicon with a high impurity concentration of germanium (9×10 ¹⁹ cm ^?3 ) depends on temperature as ν～T ^q , q≈3 at T=(5–30) K. An increase in the absolute value of the relaxation rate and a weakening of its temperature dependence are observed in samples of degenerate silicon in the given temperature range. Based on the experimental data obtained, the conclusion is made that the spin-exchange scattering of free charge carriers makes a significant contribution to the magnetic moment relaxation of a shallow acceptor center in degenerate silicon at T?30 K. Estimates are obtained for the effective cross section of the spin-exchange scattering of holes (σ _h ) and electrons (σ _e ) from an Al acceptor center in Si: σ _h ～10^?13 cm² and σ _e ～8×10^?15 cm² at the acceptor (donor) impurity concentration n _a (n _d )～4×10¹⁸ cm^?3.     

Distribution d'énergie des électrons secondaires émis par InP et GaP soumis à un bombardement d'ions Ar de 40 keV

The energy distributions N(E) of secondary electrons emitted from GaP and InP samples bombarded with 40 keV Ar⁺ ions have been studied by a retarding potential method and an electronic derivation. The spectra show beyond an intensive peak developed at 2 eV, a detailed spectrum between 80 and 140 eV. The analysis of this spectrum reveales Auger electrons corresponding to L₂₃(P) VV and L₂₃M_IV–V(Ga) V [or L₂₃(P) N_IV-V(In) V] transitions; moreover, peaks due to plasmon excitations and d band excitations can be distinguished.     

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.     

Calculation of X-ray and Auger transition rates, lifetimes, X-ray wavelengths, and fluorescence yields of variously ionized silicon atoms

X-ray and Auger transition rates, X-ray wavelengths, and fluorescence yields are calculated for variously ionized silicon atoms with configurations 1s2s^m2pⁿ, m=0-2, n=1-6. The calculation has been performed using the Hartree-Fock atomic model. Intermediate coupling and configuration interaction have been taken into account. The energies and widths are found to be strongly affected by configuration mixing. The results from the present calculation have been compared with those available in the literature. The theoretical K_α hypersatellite and satellite spectra fall into several well-separated regions, corresponding to each of the possible number of spectator electrons in the 2s and 2p shells. The dependence of radiative rates and fluorescence yields on the number of spectator electrons is also investigated.     

Electron energy loss spectra of the silicon 2p, 2s, carbon 1s and valence shells of tetramethylsilane

Inner shell excitation spectra of tetramethylsilane, (CH₃)₄Si, have been measured in the silicon 2s, 2p (L_I,II,III-shell) and carbon is (K-shell) regions using electron energy-loss spectroscopy at an impact energy of 2.5 keV and a scattering angle of ~1°. The high-resolution valence shell spectrum has also been observed at an impact energy of 3 keV and a zero degree scattering angle. The silicon 2p spectra are compared and contrasted with published photoabsorption spectra of SiF₄, SiH₄, and other related Si-containing molecules with varying ligands.     

Backscattering of low-energy (0–8 eV) electrons by a silicon surface

An experimental apparatus and method for investigating elastic and inelastic backscattering (180°) of low-energy (0–8 eV) monoenergetic electrons by a solid surface are described and the first results are presented for the reflection of electrons by samples of pure single-crystalline silicon with a polished surface (Si), doped p-type single-crystalline silicon with a porous surface (Si-p) as well as H₂O and H₂O₂ passivated porous samples, Si-p + H₂O and Si-p + H₂O₂. A structure due to the excitation of surface plasmons has been observed for the first time in the loss spectra. Features corresponding to a resonance excited state of molecular nitrogen adsorbed on the surface of porous silicon have been observed in the constant residual energy spectra. Zh. Tekh. Fiz. 67, 103–108 (May 1997)     

Contribution of the inhomogeneous waves in angular-spectrum representations

Angular-spectrum representations of wave fields separate naturally into two parts, V_h(R,t) containing only homogeneous plane waves and V_i(R,t) containing only inhomogeneous plane waves. Some properties of V_i(R,t) are presented here. We conclude that, for some problems, V_i(R,t) has several unphysical properties, and that under certain specified conditions, V_i(R,t) can not be neglected compared to V_h(R,t), even far from the sources of the field.     

Bonding and composition diagrams for sputtered a-Si : H

The combined influence of H partial pressure (p_H) and deposition rate (R_D) on Si-H bonding and total H content in diode-sputtered a-Si : H is presented in two simple graphs for the case of substrate temperature (T_s) equal to 225°C. Similar to a phase diagram, the graphs predict the H content and Si-H bonding that will result if a deposition is carried out with any prescribed pair of values (p_H, R_D), where 0.04 < p_H < 10 Paand 0.01 < R_D < 1 nm/sec. Well defined regions of Si-H bonding represented by dominant infrared stretching absorptions at 2000, 2090 and 2150 cm^?1 are obvious in the bonding diagram. The absorption at 2090 cm^?1 is the most commonly observed and is obtainable over a wide range of intermediate values of p_H and R_D. The absorption at 2000 cm^?1 is dominant only for the lowest p_H and the highest R_D. The absorption at 2150 cm^?1 is dominant in films deposited at high p_H and low R_D. The composition diagram shows that highest total H content is obtained for low R_D and high p_H, and lowest total H content results for high R_D and low p_H     

DasKLL- Auger-Spektrum von Chlor

TheKLL Auger spectrum of chlorine in CCl₄ has been investigated with an electrostatic energy analyzer. The ionization in theK shell of chlorine was caused by electron impact. Absolute energies and relative intensities of transitionsKL ₁ L ₁(¹ S,KL ₁ L _2,3(¹ P),KL ₁ L _2,3(³ P) andKL _2,3 L _2,3(¹ D) have been determined. Via the width of theK level of chlorine also experimental values of absolute transition probabilities have been calculated. While the relative intensities deviate strongly from theoretical values, the absolute transition probabilities agree better with theoretical values, especially with those calculated byRubenstein. — In an appendix the natural line widths of theKLL components of argon have been calculated theoretically.     

On the separation of initial and final state effects in photoelectron spectroscopy using an extension of the auger-parameter concept

First, we show that the quantity Δβ(i) = ΔE_A(kii) + 2ΔE_B(i) — ΔE_B(k) is directly related to the final state relaxation contribution ΔE_R(i) of the binding energy shift ΔE_B(i). ΔE_A(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell¹. It is shown that ΔR(P_2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations.     

Local structure of porous silicon studied by means of X-ray emission spectroscopy

2,3 X-ray emission spectra of porous silicon (P-Si) and of spark-processed silicon (sp-Si). Both types of Si-structure display strong photoluminescence in the visible range of the spectrum. Porous samples were prepared by anodization of n^-- and p⁺-Si-wafers. Whereas for the P-Si processed from p⁺-Si the presence of some amorphous silicon is detected, the X-ray emission spectra of porous Si prepared from n^--Si display a higher content of SiO₂. For spark-processed Si the Si L_2,3 X-ray emission spectra reveal a much stronger degree of oxidation which extends to depths larger than 10000 Å. Furthermore, the chemical state of silicon atoms of sp-Si measured at the center of the processed area is close to that of silicon dioxide, and it has an influence on the photoluminescence energy. Specifically, green photoluminescent sp-Si shows a higher degree of oxidation than the blue luminescent specimen. However, the depth of oxidation consistently decreases in areas with weak or no PL. Possible origins of the observed photoluminescence are discussed. Accepted: 6 March 1997     

Temperature dependence of ion-induced auger electron emission from (111) silicon: I. Experiments

Abstract

Measurements of both secondary electron emission coefficient γ and SiL₂₃ Auger yield ρ_A obtained from (111) Si target bombarded by high fluence of noble gas ions were performed. For Si irradiated at room temperature at doses more than 10¹⁷ ions per cm², monotonous increasing variation of γ and ρ_A versus incidence angle i was observed. For Si irradiated at a temperature more than a critical value, γ(i) and ρ_A(i) curves exhibited, superimposed to monotonous variation, some minima when the ion beam penetrates the crystal along low index directions. In the range 20–650°C, the Auger yield temperature dependence showed a sharp variation around a critical value depending on the ion mass for a given incident energy. These results are linked to an amorphous-crystalline phase transition.     

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.