Soft-landing deposition of radioactive probe atoms on surfaces

We present a method to deposit a wide range of radioactive probe atoms on surfaces, without introducing lattice damage or contaminating the surface with other elements or isotopes. In this method, the probe atoms are mass-separated using an isotope separator, decelerated to 5 eV, and directly deposited on the surface. The method allows for performing hyperfine interactions experiments using trace amounts of radioactive probes located at surfaces and interfaces. The characteristics of the deposition method will be described, with particular attention to the deceleration stage of the isotope separator. The method was tested with perturbed angular correlation (PAC) experiments on the system In on Cu(17,1,1). The results are in agreement with molecular dynamics simulations of the deposition process. New developments, in particular the study of the self-diffusion of Ag atoms on Ag(100) by means of PAC with the ¹¹¹Ag probe, are briefly discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Radioactive ions for solid-state investigations at magnetic surfaces and interfaces

Hyperfine interactions observed at isomeric states of radioactive probe nuclei are used as a tool for solid-state investigations. This method is sensitive to atomic-scale properties. In recent years surface and interface investigations using radioactive probes delivered many results which can hardly be achieved by any other method. Several groups, e.g., from Konstanz, Leuven, Groningen, Aarhus, Uppsala, Tel Aviv, Pennsylvania, contributed to this field. Our group studies magnetic properties at surfaces and interfaces performing perturbed angular correlation (PAC) measurements in the UHV chamber ASPIC (Apparatus for Surface Physics and Interfaces at CERN). We take advantage of the enhanced variety of PAC probes delivered by the on-line mass separator ISOLDE. First, we report on measurements of magnetic hyperfine fields ( B _hf) at Se adatoms on a ferromagnetic substrate using ⁷⁷Se as a PAC probe. The investigation of induced magnetic interactions in nonmagnetic materials is a further subject of our studies. Here the nonmagnetic 4d element Pd is investigated, when it is in contact with ferromagnetic nickel. An outlook will be given on studies to be done in the future. The experiments were performed at the HMI, Berlin, and at CERN, Geneva. Received: 1 May 2001 / Accepted: 4 December 2001     

Nuclear quadrupole interactions associated with adsorbed halogen and chalcogen atoms at semiconductor surfaces

As part of a program for studying hyperfine interactions at surfaces of condensed matter systems, we have studied the nuclear quadrupole interactions associated with group VI and VII atoms adsorbed on silicon surface. The electronic structures used for these investigations were determined through the self-consistent Hartree-Fock cluster procedure using sizeable clusters of atoms to simulate the infinite systems. Results will be presented for the nuclei of halogen atoms adsorbed on the silicon (111) surface and for sulfur and selenium atoms on the (110) surface.     

Spin-polarized nuclei as probes of electromagnetic field distributions on solid surfaces

Recent experiments using thermal beams of nuclear-spin-polarized alkali atoms adsorbed on hot metal surfaces show that polarized nuclei are sensitive probes of surface electromagnetic field distributions. The high polarization of the probe beams, when coupled with the efficiency of atomic physics techniques used for monitoring the polarization of desorbed particles, makes possible a variety of interesting spinrelaxation experiments on single-crystal surfaces, including nuclear magnetic resonance. Extension of the current experimental method to semiconductor and insulator surfaces at arbitrary temperatures appears to be straightforward. The information from spin-polarized nuclear surface spectroscopy (SPNSS) will allow detailed tests of charge-density profiles now available in self-consistent surface structure calculations. Moreover, the variety of presently available polarized nuclear species suggests that the chemistry of many interesting adsorbate-surface systems could also be profitably investigated by this technique. The use of spin-polarized hydrogen nuclei in particular offers enticing prospects for fundamental studies in catalysis, surface structure and basic two-dimensional physics.     

Hyperfine-interaction studies of surfaces

Applications of hyperfine-interaction techniques, like NMR, PAC and Mößbauer spectroscopy, to well-characterized surfaces are discussed and the present knowledge of surface hyperfine fields is reviewed. Measurements of nuclear spin relaxation permit to extract the local density of electron states at the Fermi level of adsorbed alkali atoms. From the observed electric-field-gradient properties surface probe sites and diffusion processes can be inferred; the experimentally determined magnetic hyperfine fields give access to the electron-spin behaviour at magnetic surfaces.     

Hyperfine interactions of impurities in defect sites in ion-implanted metals

The lattice location of ion-implanted radioactive isotopes in metals and their interactions with defects in their own radiation damage cascade are of importance for studies of the hyperfine interactions of such probe atoms by nuclear methods. Recent results from Mössbauer and PAC experiments in particular are reviewed. Emphasis is put on lattice site identifications, which can be inferred from measured lattice-dynamical and hyperfine interaction parameters of probe atoms. Some general conclusions on the hyperfine interactions in interstitial- and vacancy-type complexes are drawn.     

The short range of the electronic promoter effect of potassium

Photoemission of Adsorbed Xenon atoms (PAX) as a local work function probe is used to investigate the range of the electronic promoter effect of potassium submonolayers on a Ru(001) surface. Three Xe states on these bimetallic K/Ru surfaces are clearly distinguishable by their 5p photoemission and are associated with Xe probe atoms at basically unmodified Ru sites, at “mixed” K.Ru sites next to K ions, and on top of potassium, respectively. From the relative intensities of these three states as well as from their 5p electron binding energies as a function of potassium coverage it is concluded that the radius of the “sphere” of modified charge density around one K ion is ～ 6 Å.     

First-principles study of Ar adsorptions on the （111） surfaces of Pd, Pt, Cu, and Rh

In the present paper we give a detailed report on the results of our first-principles investigations of Ar adsorptions at the four high symmetry sites on M （111） （M =Pd, Pt, Cu, and Rh） surfaces. Our studies indicate that the most stable adsorption sites of Ar on Pd （111） and Pt （111） surfaces are found to be the fcc-hollow sites. However, for Ar adsorptions on Cu （111） and Rh （111） surfaces, the most favorable site is the on-top site. The density of states （DOS） is analyzed for Ar adsorption on M （111） surfaces, and it is concluded that the adsorption behavior is dominated by the interaction between 3s, 3p orbits of Ar atoms and the d orbit of the base metal atoms.     

Investigations of “soft-landed” Cd surface atoms via nuclear methods: hyperfine-field sign determination

Using refined preparation techniques, cadmium guest atoms have been positioned at different sites on the surfaces of nickel crystals. The magnetic hyperfine fields and the electric field gradients at the Cd nuclei were measured by time-dependent perturbed angular correlation (TDPAC) spectroscopy of the emitted gamma radiations. By measuring the combined interactions, electric field gradients and magnetic hyperfine fields can be unambiguously attributed to each surface site. The signs of the magnetic hyperfine fields are determined by applying an external magnetic field and choosing the appropriate γ-ray detector configuration. The measured fields correlate with the number of neighbouring host atoms. Band structure calculations confirm this finding and predict magnetic fields for various sp elements from the band structure of the s-like conduction electrons. The quadrupolar interactions are manifestations of the balance in the occupation of the guest p-sublevels. These results provide new information on the structure and formation of electronic configurations of sp elements in different local environments and will contribute to understanding electronic effects on surfaces.     

Adsorption sites of111In and111mCd on Pd(111) surfaces characterized by the electric field gradient

PAC measurements of the electric field gradient at the nucleus of isolated probe atoms on Pd(111) surfaces lead to the identification of five adsorption sites successively occupied by the parents¹¹¹In and^111mCd during annealing between 80K and 600K. The data are consistent with an estimated activation energy for Pd surface self diffusion of E_a=0.76(8)eV.     

Cavity formation at indium impurities in bcc metals

The defect formation in the bcc metals W and Mo above annealing stage III and the influence of rare gases on this process were investigated by means of the perturbed angular correlation technique using¹¹¹In as radioactive probe. In both metals a relatively high electric field gradient (EFG) could be observed at the indium site, characterized by the quadrupole interaction frequencies υ_Q=263 MHz, ν=0 and υ_Q=220 MHz, ν≈0.15 for W and Mo, respectively. The observations are assigned to the growth of threedimensional vacancy clusters at the probe atoms with the indium atoms situated in the inner surface of this cavities, thus experiencing the corresponding surface EFG.     

KMM Auger transitions in atoms having 46 ⩽Z ⩽ 84

The results of investigations of KMM Auger transitions in atoms having 46 ?Z ? 84 are discussed. All experimental data were obtained by studying the spectra of electron irradiation accompanying the decay of radioactive nuclei. Comparison of the experimental data is made with existing calculations of the energies and intensities of KMM transitions. Requirements for an adequate theory of the intensities of these transitions are formulated.     

Chemisorption of isolated Br atoms on Si(100)-(2 × 1) studied by PAC

Chemisorption and desorption of isolated bromine adatoms on the Si(100)-(2 × 1) surface were investigated with nuclear methods. Br adsorption sites at low coverages of 10⁻³ monolayers (ML) were characterised by measuring the nuclear quadrupole interaction with perturbed γγ-angular correlation (PAC) of ⁷⁷Br→⁷⁷Se probe atoms. Below room temperature, two distinct adsorption sites for Br are revealed by PAC. One of them disappears after isochronal annealing above 300 K. The more stable probe-atom state is associated with single Br atoms saturating a dangling bond of the surface, while the less stable state is attributed to adsorption of Br at a bridge site. The potential barrier between the two adsorption sites is estimated to be 0.9(1) eV. At temperatures above 550 K, the fraction of atoms on distinct sites decreases, presumably due to surface diffusion. By measuring the γ-activity of the sample, complete desorption of the ⁷⁷Br atoms was observed above 620 K.     

Direct observation of individual atoms on metals

The ability to observe the structure of surfaces and to monitor the processes occurring on them with atomic resolution is crucial to a better understanding of surface properties. The field ion microscope provides this capability routinely, and with the atom probe the chemical identity of single atoms can be ascertained as well. Recent work with these techniques, aimed at a better understanding of atomic events on metal surfaces, will be reviewed with special emphasis on the following topics: (1) Observation of atomic binding sites. (2) Interfacial structure. (3) Chemical analysis on the atomic level. (4) Determination of binding energies. (5) Atomic events in surface diffusion.     

Electric field gradient at111In on Cu (100) surfaces and its utilization for indium surface diffusion

The electric field gradient at¹¹¹In probe atoms on Cu (100) surfaces was studied. At clean surfaces all probes are exposed to a well-defined surface field gradient. This is used to investigate indium surface diffusion, where the applied PAC method allows to observe diffusion steps on an atomistic scale. The jump rate for indium on Cu (100) was found to be in the order of 10^–3 Hz at 200 K.     

Deep level transient spectroscopy on radioactive impurities: Demonstration for Si:111In*

A defect specific analysis technique is introduced that combines the high concentration sensitivity of deep level transient spectroscopy (DLTS) with the radioactive transmutation of probe atoms; this technique results in the chemical identification of particular atoms which participate in the observed defect centres. The method is demonstrated for n- and p-type silicon samples, which are implanted with radioactive ¹¹¹In* ions. The activity of the indium ions decreases with half-life T _1/2 of 2.83 d by a decay into stable cadmium ions. A series of Cd-related levels whose concentrations increase exponentially with the decay time of ¹¹¹In* are identified in the DLTS spectra. Cd-diffused silicon samples are investigated for comparison; these samples reveal similar DLTS spectra. The analysis method described can be extended to all semiconductors and to a variety of radioactive probe atoms.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

Mössbauer spectroscopy at ISOLDE

Applications of radioactive ion beams produced at the ISOLDE facility for Mössbauer studies of probe atoms in solids are presented. Examples are given for a site-selective incorporation on different substitutional sites in compound semiconductors by ion implantation and thermal annealing of the radiation damage resulting from the implantation. The interactions of the probe atoms with lattice defects created in the implantation process have been studied to elucidate likely causes for the site-selective implantation mechanism. The technique has enabled to determine the electronic densities at electrically active substitutional probe atoms, having shallow donor or acceptor states as well as states deeper in the band gap. The results are in good agreement with theoretical results from local density calculations. Methodological aspects of the Mössbauer emission techniques employed at ISOLDE are compared to alternative accelerator based techniques and the consequences of the application of different precursor isotopes to the ⁵⁷Fe Mössbauer isotope are treated in detail for ⁵⁷Fe in silicon. Finally, results obtained for the magnetic hyperfine interactions of 5 sp impurities associated with vacancies in ferromagnetic metals are discussed.     

Chemisorption and surfaces studied by nuclear magnetic resonance spectroscopy

This paper presents an introduction to the study of surfaces and chemically adsorbed species with nuclear magnetic resonance (NMR) spectroscopy. The analysis is based on nuclear magnetic interactions in the solid state: dipole-dipole couplings, chemical shift anisotropy, Knight shifts, and quadrupolar splitting. The physical origins and characteristics of each interaction, as well as relative intensities for different nuclei, are discussed. In particular, emphasis is placed on the relation of these interactions to quantities of interest to studies in adsorption and catalysis: motional properties of the adsorbate, the distribution of adsorption sites, the chemical state of atoms adsorbed at the surface, electrostatic field gradients, and the metallic character of surface atoms. Techniques to observe these interactions are described; subdivided by the type of nucleus: strongly coupled nuclei (e.g. ¹H, ¹⁹F), weakly coupled nuclei (e.g. ¹³C, ¹⁵N, ²⁹Si, ¹⁹⁵Pt), and quadrupolar nuclei (e.g. ²H, ¹⁴N, ²⁷Al). The techniques described to isolate and identify the overlapping effects in the spectra include multiple-pulse spin echoing and decoupling, double-resonance irradiation, multiple-quantum excitation, and mechanical sample spinning. A review of the recent application of these techniques to studies of adsorption and surfaces illustrates the potentials and limitations. Finally, a procedure for formulating a NMR study of surface samples is proposed, with respect to sample composition and character, and the type of information desired.     

Subsurface dimerization in III-V semiconductor (001) surfaces

We present the atomic structure of the c(8 x 2) reconstructions of InSb-, InAs-, and GaAs-(001) surfaces as determined by surface x-ray diffraction using direct methods. Contrary to common belief, group III dimers are not prominent on the surface, instead subsurface dimerization of group III atoms takes place in the second bilayer, accompanied by a major rearrangement of the surface atoms above the dimers to form linear arrays. By varying the occupancies of four surface sites the (001)-c(8 x 2) reconstructions of III-V semiconductors can be described in a unified model.     

Ba和Sr原子在ZnO(0001)表面吸附的密度泛函理论研究

我们采用密度泛函理论下的平面波赝势方法研究Ba和Sr原子在ZnO(0001)表面的吸附结构和性质,仔细研究了三个吸附位（T4, H3 and Top）。发现Ba和Sr吸附在表面的H3和T4位时,他们之间的结合能相差很小,且这两种金属更易于吸附在表面的T4位,我们把计算的结果与贵金属在ZnO(0001)表面的吸附行为及前人的实验结果进行了比较,理论上发现Ag和Au易于吸附在ZnO(0001)表面的H3位,而实验上观察到即使在很小吸附比的条件下ZnO(0001)表面上也能形成Cu的团簇结构,这主要是由于Cu和ZnO(0001)表面衬底强的相互作用所致。