Role of excitons in electron- and photon-stimulated desorption of neutrals from alkali halides

Low-energy (5-15 eV) electron- and photon-stimulated desorption of KI(100) yields I2P3/2 and 2P1/2 with hyperthermal (0.3 eV) and thermal velocity components. The desorption threshold for both components is 5.3 eV and is correlated with the gamma3/2-exciton long-wavelength edge. Exciton decay at the surface directly produces I2P3/2 and 2P1/2 with hyperthermal velocity and is in competition with self-trapping. Spin memory of the gamma-exciton hole-component is also evident in the hyperthermal channel. An exciton mediated desorption mechanism is presented which is general in alkali halides.     

Cross sections for electron-stimulated desorption of alkali-metal atoms from adlayers on oxidized tungsten

Earlier cross-section measurements of electron-stimulated desorption (ESD) of Li, Na, K, and Cs atoms from adlayers on oxidized tungsten are analyzed with respect to substrate temperature and degree of oxidation. It is conjectured that the ESD cross sections are determined by the ratio of the rates of neutral alkali-metal re-ionization on the surface and of relaxation of the O⁺ charge in the substrate. A comparison with experiment revealed the dependence of the re-ionization rate of an alkali-metal adatom on its size and mass, as well as the dependence of the O⁺ charge relaxation rate on substrate temperature and degree of oxidation. The relation of the charge relaxation time to the substrate band structure is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1491–1497 (August 1997)     

Negative photoplastic effect due to the relaxed excited state of the F-center in alkali halides

Abstract

To make clear the mechanism of the photoplastic effect (PPE) in alkali halides containing F-centers, on the basis of the photochemical reaction of the F-center, temperature dependence of the PPE in KC1, and KBr and NaCl was studied from 95 K up to RT. The characteristic critical points θ _ts in colored KC1 and KBr were determined to be 110 and 190 K, respectively. Below θ _t the sign of the PPE in both crystals was negative, i.e., decrement of the flow stress during light illumination was observed. Moreover, the θ _ts were in good agreement with the temperature where the photoconductivities show remarkable increase in the course of the measurements. The negative PPE is explained in terms of the rotation of the principal strain axis of the relaxed state of the F-center having ?100? tetragonarity as to relax the stress around the edge dislocation coming closely.     

Surface topography dependent desorption of alkali halides

Electron-stimulated desorption of the (100)KBr surface has been investigated in vacuum with noncontact atomic force microscopy and mass spectroscopy. It has been found that both desorption components (K and Br) show oscillatory dependence on the electron dose with the oscillation amplitude decaying gradually. These results correspond with periodically varying, as a result of a layer-by-layer desorption, surface topography. It is proposed that the surface terrace edges act as traps for excited F centers diffusing in the crystal. The oscillating density of terrace edges varies surface recombination/reflection rates for the F centers and modulates the balance between surface and bulk deexcitation of the crystal.     

Energy distribution of alkali-metal atoms under electron-stimulated desorption from the surface of oxidized refractory substrates

An analysis is made of experimental data on the dependence of the energy distributions of Li, Na, and Cs atoms emitted in electron-stimulated desorption on their concentration on the surface of oxidized tungsten and molybdenum substrates.     

Application of synchrotron radiation to investigation of the mechanism of increase in the yield of alkali metal ions in electron-stimulated desorption

Core-level photoelectron spectroscopy with synchrotron radiation (hv = 140 eV) has been applied to study the variation in the Si⁺ charge state in silicon films deposited on the W(100) surface after thermal annealing of the substrate. The purpose of this study is to check the mechanism responsible for the sharp increase in the yield of Na⁺ ions in electron-stimulated desorption from a sodium layer adsorbed on the Si/W(100) surface after high-temperature annealing. The evolution of the W 4f _7/2 and Si 2p photoelectron spectra and the valence band photoemission spectra is investigated for two silicon coverages (1 and 3 ML) on the W(100) surface in the temperature range 300<T<2200 K. It is shown that annealing of 1 ML Si on the W(100) surface results in the formation of a W-Si covalent bond, which can weaken the Si-Na bond and lead to an increase in the equilibrium distance X ₀ and, hence, to an increase in the yield of Na⁺ ions in electron-stimulated desorption. The variation in the photoelectron spectra under annealing of 3 ML Si differs from that observed after annealing of 1 ML Si in the direction of charge transfer, thus correlating with the opposite effect of annealing of 3 ML Si/W on the Na⁺ yield in electron-stimulated desorption.     

Anomalous F-center distribution in alkali halides irradiated with 1.5-MeV protons to high fluences

Crystals of KCl and KI irradiated to fluences of the order of 10¹⁶ protons/cm² exhibit an anomalous dip in F-center profile near the end of the proton penetration depth. This effect is shown to arise from the destruction of F centers by hydrogen capture, forming U centers in a distribution whose peak coincides with the proton range.     

Dislocation motion in photomechanical effects and the lifetime of photochemical products of the F-center in alkali halides

A simple theory describing photomechanical effects in colored alkali halides was proposed based on statistical dislocation dynamics. From the present theory together with empirical data on photomechanical measurements, the lifetime of the F^--center in KCl is found to be about 2 s at around RT and the relevant activation energy is 0.29 eV.     

Nonlinear electric properties of alkali metal halides

The first and second hyperpolarizabilities as well as the dipole moments and dipole polarizabilities are studied for a series of the alkali metal halides (MeX, Me = Li, Na, K, X = F, Cl, Br). The static results have been calculated at various levels of including the electron correlation contribution. The frequency-dependent data for different nonlinear optical processes correspond to TDHF calculations and can be approximately scaled for the electron correlation contribution. The present study also gives a systematic comparison of the performance of the so-called Pol basis sets and the recently developed basis sets (HyPol) designed for calculations of electric hyperpolarizabilities. Several regularities in the calculated data are observed and discussed in terms of ionic models supplemented by the electron density confinement effect. For some of the studied systems the first and second hyperpolarizabilities are found to have interestingly high values, comparable to those for molecules used in nonlinear optical materials.     

Electron-stimulated desorption of rare-earth metal atoms

The yield of europium and samarium atoms in electron-stimulated desorption from layers of rare-earth metals (REMs) adsorbed on the surface of oxidized tungsten has been measured as a function of the incident electron energy, surface coverage by REMs, degree of tungsten oxidation, and substrate temperature. The measurements were performed using the time-of-flight method with a surface-ionization-based detector within the substrate temperature interval 140–600 K. The yield studied as a function of electron energy has a resonance character. Overlapping resonance peaks of Sm atoms are observed at electron energies of 34 and 46 eV, and those of Eu atoms, at 36 and 41 eV. These energies correlate well with the REM 5p and 5s core-level excitation energies. The REM yield is a complex function of the REM coverage and substrate temperature. The peaks due to REM atoms are seen at low REM coverages only, and their intensity usually passes through a maximum with increasing coverage and substrate temperature. The concentration dependence of the REM atom yield is affected by the deposition of slow Ba⁺ ions, but only if they are deposited after the REM adsorption. At higher REM coverages, additional peaks are observed at electron energies of 42, 54, and 84 eV, which originate from excitation of the 5p and 5s tungsten levels and result from desorption of SmO and EuO molecules. The temperature dependence of the intensity of these peaks is explained to be due to the order-disorder phase transition. The desorption of REM atoms is the result of their reversed motion through the adsorbed REM layer, and the SmO and EuO molecules desorb due to the formation of an antibonding state between the REM oxide molecules and the tungsten ions.     

Initial ion velocity in electron-stimulated desorption

The effect of electronic-shell repulsion and electron-phonon interaction among atoms of an adsorption complex on the initial ion velocity is considered.     

Transient species in radiolysis of melted alkali metal halides

There are very few data on the radiation chemistry of ionic liquids. The most interesting problem in this field is the nature of transient species. For this purpose we have studied some melted alkali metal halides by pulse radiolysis method with optical detection of short-lived species.     

Effect of deposition of samarium atoms on the electron-stimulated desorption of cesium and samarium atoms from the surface of tungsten coated by gold and cesium

It has been shown that deposition of Sm atoms on W(100) surface coated by several monolayers of gold and cesium affects noticeably the yield of Cs atoms in electron-stimulated desorption (ESD) from this surface. The measurements have been performed by the time-of-flight method with a surface-ionization detector. The paper reports on the first observation of ESD of Sm atoms from the tungsten surface coated by layers of gold and cesium. The ESD threshold for Sm atoms, E _e = 57 eV, coincides with that for Cs atoms and corresponds to the energy of the Au 5p _3/2 core level. The dependence of the ESD yield of Sm atoms on the bombarding electron energy E _e follows a resonance pattern in the form of a narrow peak located in the range 57 ≤ E _e ≤ 66 eV. Deposition of Sm atoms at room temperature (～300 K) reduces (by a factor of about two) the ESD yield of Cs atoms for 600 s, and deposition of Sm atoms at 160 K reduces the ESD of Cs atoms down to zero already for 270 s. This difference finds explanation in the study of the change the structure of the top layer of the (Au + Cs)/W surface coating undergoes under cooling of the surface from 300 to 160 K.