Probability of ionization of sputtered particles as a function of their energy: Part I: Negative Si ions

In this study we have investigated how the probability of ionization of sputtered Si atoms to form negative ions depends on the energy of the atoms. We have determined the ionization probability from experimental SIMS energy distributions using a special experimental technique, which included de-convolution of the energy distribution with an instrumental transmission function, found by separate measurements.We found that the ionization probability increases as a power law ∼E^0.677 for particles sputtered with energies of 0-10 eV, then becomes a constant value (within the limits of experimental error) for particles sputtered with energies of 30-100 eV. The energy distributions of Si⁻ ions, measured under argon and cesium ion sputtering, confirmed this radical difference between the yields from low and high-energy ions.To explain these results we have considered ionization mechanisms that are different for the low energy atoms (<10 eV) and for the atoms emitted with higher energy (>30 eV).     

A quantum-mechanical model for the ionization and excitation of atoms during sputtering

A quantum-mechanical model is developed for the process by which an atom is excited or ionized as it is sputtered from a metal surface. The probability of excitation is given by R = (A/ΔE)²(hv/aΔE)ⁿ, where A is the binding energy of a surface atom before sputtering, v is its average velocity after sputtering, a is the thickness of the surface, and Δ E the excitation energy. For ionization, ΔE = I?φ, with I the ionization energy of the sputtered atom, and φ the work function of tke surface. Available experimental data for ionization are fitted best with a = (1.4 ± 0.3)A?, and n = 2.5 ± 0.3. The model is expected to be applicable to bombarding energies up to about 100 keV.     

Energy dependence of the ionization probability of sputtered Cu and Ni

Despite its great sensitivity, the usefulness of secondary ion mass spectrometry (SIMS) for many applications has been limited by an inadequate understanding of the probability of sputtering an atom in an ionized state. To determine this ionization probability for clean Cu and Ni surfaces, I have measured the energy distribution of sputtered neutrals and ions by quadrupole mass filtering and retarding potential analysis using potential modulation differentiation. Analysis of sputtered neutrals was accomplished by electron impact ionization. Because the neutrals outnumber the ions by at least two orders of magnitude, the ratio of sputtered ions to neutrals is an accurate measure of the ionization probability. For energies below 20 eV the dependence of the ionization probability on energy goes as P(E) α Eⁿ, where n = 0.65 for clean Cu. The absorption of oxygen on the Cu surface increases the total ion yield while causing a reduction in the value of the exponent n. Similar results are found for nickel, where n = 0.54 for the clean surface.     

Model of ionization of atoms sputtered from solids

A new microscopical quantum-mechanical model of ionization of sputtered particles is described which takes into account electron excitations due to the atomic motions in the substrate. The substrate is represented by a simple atomic, metal-like, chain. Numerical calculations yield ionization probabilities R⁺ which have magnitudes close to the experimental values and have realistic velocity dependence. The function of R⁺ versus the sputtered atom ionization energy can be well approximated by the Maxwell-Boltzmann law with an effective temperature of about 3500 K.     

Ionization probability of sputtered particles as a function of their energy: Part II. Positive Si ions

In this paper we represent the experimental ionization probability of sputtered silicon atoms as a function of their energy, which has been obtained for positive Si⁺ ions sputtered from silicon by O₂⁺ ion beam. To explain the experimental data, we have considered ionization of an outgoing atom at a critical distance from the surface, which occurs due to the electron transition between this atom and the surface, and suggested the formation of a local surface charge with the polarity opposite to that of the outgoing ion that has just been formed. Then we have considered the interaction between those two charges, outgoing ion, and surface charge as a process of the particle passage through a spherical potential barrier; as a result, we have obtained the theoretical energy distribution of secondary ions. Together with the well-known Sigmund-Thompson energy distribution of sputtered atoms, the obtained ion energy distribution allowed us to derive the equation for the secondary ion yield versus the sputtered particle energy. Both equations derived have exhibited a quite good correlation with our experimental results and also with a large number of published experimental data.     

Dependence of scattered ion yield on the incident energy: Ne on pure gallium and indium

An experimental study of the ion yield dependence on the incident energy (0.4-2.2 keV) for Ne⁺ isotopes scattered at 120° from pure gallium and indium targets has been carried out by mass-resolved ion-scattering spectrometry. For both two targets, the ion yield curves exhibited a broad maximum below 0.8-1 keV (with a lower position for Ne⁺ on In) followed by a monotonous decrease yield without any oscillatory features. The energy dependence of ion-survival probability was explained as a complex interplay of the Auger neutralization with the characteristic velocity v_c=(0.9±0.1)×10⁷ cm/s for Ne⁺ on Ga, and the collision-induced neutralization and reionization. The later ones were significant processes at the energies larger than 0.8-1.0 keV or, in terms of the distance of closest approach, d?0.5-0.55 Å; the collision-induced neutralization was more effective than the inverse process. No visible influence of isotope effect on charge exchange was found. The ion-survival probability versus the inverse ion velocity displayed an independence on the mass of Ne⁺ projectiles.     

Structure and thermal stability of AgCu chiral nanoparticles

Theoretical studies of electron impact double ionization cross sections of Ne⁵⁺ and Ne⁶⁺ ions have been performed in the binary encounter approximation (BEA). Direct double ionization (DDI) has been investigated in the modified double binary encounter model. The K-shell ionization cross sections have been also calculated in the BEA to take into account the contributions to double ionization from the ionization-autoionization (IA) process. The effect of the Coulombic field of the target ion on the incident electron has been considered in the present work. Accurate expression of σ _ΔE (cross section for energy transfer ΔE) and the Hartree-Fock (HF) velocity distributions for the target electrons have been used throughout the calculations. The present results are in overall moderate agreement with the experimental observations. Possible reasons behind the discrepancies between the theory and the experiment have been discussed.     

Multiphoton ionization of iodine atoms and CF<Subscript> 3</Subscript>I molecules by XeCl laser radiation

We report about effective ionization of iodine atoms and CF₃I molecules under the action of intense XeCl laser radiation (308 nm). The only ion fragment resulting from the irradiation of the CF₃I molecules is the I⁺ ion. We have studied the influence of the intensity, spectral composition, and polarization of the laser radiation used on the intensity of the ion signal and the shape of its time-of-flight peak. Based on the analysis of the results obtained, we have suggested the mechanism of this effect. The conclusion drawn is that the ionization of the iodine atoms by the ordinary XeCl laser with a nonselective cavity results from a three- (2 + 1)-photon REMPI process. This process is in turn due to the presence of accidental two-photon resonances between various spectral components of the laser radiation and the corresponding intermediate excited states of the iodine atom. The probability of ionization of the atoms from their ground state I(²P_3/2) by the radiation of the ordinary XeCl laser is more than two orders of magnitude higher than the probability of their ionization from the metastable state I^*(²P_1/2). The ionization of the CF₃I molecules by the XeCl laser radiation occurs as a result of a four-photon process involving the preliminary one-photon dissociation of these molecules and the subsequent (2 + 1)-photon REMPI of the resultant neutral iodine atoms.     

Study of the energy level structure for the isoelectronic series of scandium-like ions

The structure of the energy level system for 39 ions of the scandium isoelectronic sequence is studied on the basis of the relativistic self-consistent field method taking into account the configuration interaction. The Dirac-Fock equations are solved with subsequent diagonalization of the energy matrix. The ground-state ionization potentials are determined for each ion. The energy levels corresponding to the 3d4s ², 3d ²4s, and 3d ₃ configurations are also calculated. The obtained energy values are compared with the experimental data as well as with the results of calculations carried out by other authors.     

Multiphoton fragmentation and ionization of CF2HCl molecules and clusters by UV radiation

The results of experimental studies of multiphoton ionization of CF₂HCl molecules and clusters by UV laser radiation in the wavelength range 217–236 nm are reported. In the case of molecules, the main reaction products are CF₂H⁺ and CF⁺ ions as well as atomic chlorine. It is found that the spectra of the products of ionization of free molecules and molecules condensed into clusters differ qualitatively: multiphoton ionization of clusters does not yield CF₂H⁺ ions. The dependences of the ion yield on the intensity of laser radiation and its wavelength are measured. The effect of a constant electric field and the radiation spectral width on the multiphoton ionization process is demonstrated. The shape of the velocity distributions is determined for a number of products. A strong anisotropy is detected in the reaction of formation of CF₂H⁺ ions. Possible mechanisms for these processes are discussed.     

The theoretical and experimental study of the ionization processes during the low energy ion sputtering

The process by which atoms are ionized as they are sputtered from a metal surface has been analyzed both theoretically and experimentally. In the theoretical part the expressions for ionization coefficient R⁺ of atoms having the ionization energy much larger than the metal work function have been derived using a molecular orbital method. The effect of the level crossing was estimated in an approximate way. In the experimental part the SIMS experiments on clean Ni and Al surfaces and on Ni surface covered with a submonolayer of adsorbed K, Na and Al are reported. It has been found and it is for the first time reported that the energy distribution of ions sputtered from a submonolayer of adatoms is independent of energy (200–2500 eV) and mass (Ar⁺ Xe⁺ of incident ions and depends only upon the adsorption energy of the adatom. The energy distribution of ions sputtered from bulk samples has been found dependent on the primary ion energy. The measurement of the absolute value of R⁺ has shown that there is a strong correlation between the number of the adatom valence d-electrons and the value of R⁺, the value of R⁺ being smaller for atoms with more d-electrons. These experimental data have been compared with the theoretical expressions and the important role of the mechanism which takes into account the bending of the adatom energy level has been assessed.     

Analysis of energy distributions for molecular and cluster secondary ions

Energy distributions of positive ion species sputtered from various target materials have been studied in terms of the exponent of N of E^?N in the high energy part. The N value of physically sputtered ion species had a linear relationship extending over a wide range of mass numbers for both homo- and hetero-nuclear molecules, while a trunk-branch relationship with the parent ion species was observed for chemically sputtered ion species. The same significant relationship was discovered for the rearranged experimental data obtained by others.     

Resonance ionization spectroscopy of thorium

Here we describe experiments aimed at developing an element-selective ion source for thorium (Th). The technique applied is resonance ionization spectroscopy (RIS) with a thermal atom beam. Ionization schemes for isotopically nonselective ionization of Th as well as for isotopically selective ionization of ²³⁰Th are proposed. The RIS-scheme used is two-photon two-colour ionization with excitation in the ultraviolet spectral range between 244 nm and 267 nm or in the visible spectral range between 485 nm and 529 nm. Ionization of the excited atoms is performed either by ultraviolet photons or by visible photons, depending on the energy required for this process.     

Effective threshold energy for pair production in nonpolar semiconductors

A streaming model (high field) analysis is given for the average energy for and the probability of electron-hole pair production in a semiconductor when a quadratically energy dependent impact ionization cross-section exists above a threshold energy and competes with a nonpolar optical phonon scattering mechanism. A power series expansion method and tabulated results are provided to treat the resulting probability integrals of the form ∫₀^∞xⁿ exp {?(βx + x³)}dx.     

Double ionization of Sc<Superscript>+</Superscript>ions by electron impact

Electron impact double ionization cross-sections of Sc⁺ions have been calculated in the binary encounter approximation (BEA). Accurate expression of σ_ΔE(cross-section for energy transfer ΔE) and Hartree-Fock velocity distributions for the target electrons have been used throughout the calculations. Direct double ionization from ejection of 3d and 4s electrons has been investigated in the modified double binary encounter model incorporating the focusing action of the target ion on the incident electron. The identification of the 3p shell whose ionization provides a major contribution to double ionization through ionization-autoionization is an interesting aspect of the present investigation. The theoretical results show satisfactory agreement with the experimental observations.     

Single and double ionization of neon 2s- and 2p-subshells by proton and electron impact

Absolute single and double ionization cross sections of neon 2s- and 2p-subshells for proton (40–900 keV) and electron impact (0.2–10 keV) have been measured using photon spectroscopy in the spectral range of the vacuum ultraviolet. Cross sections for double ionization decrease more rapidly with increasing impact energy than cross sections for single ionization. No definite asymptotic energy dependence of a Bethe-Fano-plot could be found for double ionization in contrast to single ionization. The experimental results are compared with theoretical predictions of the shake-off model and Gryzinski's classical binary encounter theory. Better agreement is found with the latter, indicating that successive binary collisions have to be considered as a strong mechanism for double ionization by protons or electrons of the investigated energy range. Comparison is made with other experimental results for double ionization by photon impact or capture ionization by proton impact.     

Resonance three-photon ionization of samarium atom by laser radiation in the range from 17200 to 17900 cm−1

For the first time, three-photon ionization of a samarium atom in the spectral range between 17200 and 17900 cm^?1 was studied. More than 300 peaks with different amplitudes and shape are revealed in the spectral efficiency of the Sm⁺ ion formation. The majority of peaks observed is attributed to two-photon excitation of the bound even-parity states in the energy range above 35780 cm^?1. The energies and the total momenta of the states are determined.     

Nonlinear theory of multiphonon relaxation of excited rare-earth ions in laser crystals

A general formula for the probability of multiphonon nonradiative transitions between J multiplets of 4f ^N states of trivalent rare-earth ions in a crystal derived for a nonlinear mechanism is discussed. A technique is developed for calculating the quantities involved in this formula. Particular attention is given to calculating the spectral density J ^(p)(Ω), which is the Fourier transform (at the transition frequency) of the pth power of the correlation function K(t) of host ion displacements. Based on the central limit theorem from probability theory, an approximation is proposed for the spectral density J ^(p)(Ω). The theoretical values of nonradiative multiphonon transition rates are compared with experimental ones.     

L-shell vacancy production in Ag,Ta and Au for incident ionsZ 1≦10 in the energy range of 0.125–4 MeV/amu

Absolute Ag, Ta and AuL-shell X-ray cross sections were measured using protons,⁴He,¹⁴N as well as²⁰Ne ions in the energy range of 0.125–4 MeV/amu. By means of single-hole fluorescence yields experimental ionization cross sections were deduced and compared with calculations according to the corrected PWBA model — PWBA(BPCR). With decreasing asymmetry of the collision system the experimental cross sections exceed the predictions of the direct ionization theory. This is caused by an increasing contribution of a competing KL charge exchange mechanism which was investigated in detail for Ne+Ag. The Lapicki and Losonsky capture model was found to fail at energiesE<1 MeV/amu because adiabatic relaxation effects in the projectileK-shell become important. An estimation by means of the Nikitin model led to more physically comprehensible results at the lowest ion velocities investigated.     

Secondary-ion emission from clean and oxygen-covered beryllium surfaces: II. Energy dependence

The secondary-ion energy distribution obtained by sputtering clean and oxygen-covered Be has been analyzed in terms of competing processes in secondary ion emission. The ion energy distribution N⁺(E) has been separated into an ionization coefficient R⁺(E) and a total energy distribution, N(E), i.e. N⁺(E) = R⁺(E) N(E). Experimentally, the dependence of R⁺(E) on both energy and oxygen coverage indicated a linear superposition of adiabatic tunneling and resonanance ionization processes from clean and oxygen-covered portions of the surface with no contributions to the secondary-ion yield from regions of intermediate coverage. Total energy distributions of sputtered Be atoms have been deduced and the principal features agree with the predictions of the collision cascade sputtering model. Variations of the energy distributions with oxygen coverage are in accord with small changes expected in the surface binding energy as a result of surface oxidation.