Cross section and resonance effects in photoemission from Sn-doped In2O3(111)

Photoemission spectra of Sn-doped In₂O₃(111) have been measured using a range of photon energies between 40 and 1300 eV. The intensity of structure at the bottom of the valence band associated with states of mixed Sn 5s/O 2p character increases with increasing photon energy relative to that of states of more dominantly O 2p character at the top of the valence band, as expected from one electron ionisation cross sections. In addition a pronounced resonance in the intensity of a weak conduction band feature is observed around the In 4p core threshold.     

Ultrathin Y2O3(111) films on Pt(111) substrates

The growth of ultrathin films of Y₂O₃(111) on Pt(111) has been studied using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS), and low energy electron diffraction (LEED). The films were grown by physical vapor deposition of yttrium in a 10^? 6 Torr oxygen atmosphere. Continuous Y₂O₃(111) films were obtained by post-growth annealing at 700 °C. LEED and STM indicate an ordered film with a bulk-truncated Y₂O₃(111)–1 × 1 structure exposed. Furthermore, despite the lattices of the substrate and the oxide film being incommensurate, the two lattices exhibit a strict in-plane orientation relationship with the [11?0] directions of the two cubic lattices aligning parallel to each other. XPS measurements suggest hydroxyls to be easily formed at the Y₂O₃ surface at room temperature even under ultra high vacuum conditions. The hydrogen desorbs from the yttria surface above ~ 200 °C.     

Temperature dependence of the hyperfine fields of 111In in sapphire (Al2O3) single crystals

Cr has been added to FeCo substituting 10 at.% of Co or Fe in the alloy. The alloys Fe₅₀Co₄₀Cr₁₀, Fe₄₀Co₅₀Cr₁₀ and Fe₅₀Co₅₀ were prepared by mechanical alloying for 2, 5, 10, 20, 40 and 60 h. The formation of the alloy and the incorporation of the elements have been followed by X-Ray Diffraction (XRD) and Mössbauer Spectroscopy. The kinetics of mixing occurs by incorporation of Co and Cr into the Fe structure. After prolonged milling it seems that Cr incorporates itself into both $\upalpha $ -Fe and $\upalpha $ -FeCo structures and a mixture of FeCoCr rich in Cr and FeCoCr rich in Co solid solutions is obtained.     

Structural and electronic properties of Fe3O4/graphene/Ni(111) junctions

The Fe₃O₄(111)/graphene/Ni(111) trilayer is proposed to be used as an ideal spin‐filtering sandwich where the half‐metallic properties of magnetite are used. Thin magnetite layers on graphene/Ni(111) were prepared via successive oxidation of a thin iron layer predeposited on graphene/Ni(111) and the formed system was investigated by means of low‐energy electron diffraction and photoelectron spectroscopy. The electronic structure and structural quality of the graphene film sandwiched between two ferromagnetic layers remain unchanged upon magnetite formation as confirmed by experimental data.

     

Electric field gradients of111Cd in the hexagonal (A-phase) La2O3 and Nd2O3 sesquioxides

Perturbed angular correlation measurements of¹¹¹In in hexagonal La₂O₃ and Nd₂O₃ yield well defined symmetric electric field gradients with coupling constantv _Q =280 MHz (extrapolated) in La₂O₃ andv _Q =269 MHz for Nd₂O₃ at room temperature. The coupling constant in La₂O₃ linearly decreases with temperature. The spectra of La₂O₃, strongly damped at RT, rise to full amplitude at 870 K indicating dynamical interactions.     

Reactive wetting: H2O/Rh(111)

First-principles calculations imply that neither H2O bilayers nor half-dissociated, H2O+OH+H monolayers are thermodynamically stable on clean Rh(111). Thus, the experimental observation that Rh(111) supports a periodic 2D water adlayer needs an explanation. Chemistry involving common surface impurities, notably C atoms, may be the answer. Calculations show they provide favorable binding sites for H atoms detached from H2O. The resulting OH fragments can anchor a 2D water layer to the surface.     

First-principles study of the α-Al2O3(0001)/Cu(111) interface

Adhesive energetics and interfacial electronic structures have been computed from first principles for the Cu/Al₂O₃ interface. Recent transmission electron microscopy results of Cu grown by molecular beam epitaxy on Al₂O₃(0001) were helpful in modelling the interfacial atomic structure. We found that Al₂O₃(0001) relaxation effects can lower the work of adhesion W _ad by over a factor of 3. Our computed W _ad value is in reasonably good agreement with experiment, being somewhat larger, as expected from our assumption of a coherent interface. One might begin to understand this metal/ceramic adhesion as a competition between Cu and Al for oxide formation, which is easily won by Al. However this simple picture is complicated by several indications of a significant metallic/covalent component to the Cu/Al₂O₃ adhesive bond.     

Adsorption of H2O on Al(111)

The adsorption of H₂O on Al(111) has been studied by ESDIAD (electron stimulated desorption ion angular distributions), LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and thermal desorption in the temperature range 80–700 K. At 80 K, H₂O is adsorbed predominantly in molecular form, and the ESDIAD patterns indicate that bonding occurs through the O atom, with the molecular axis tilted away from the surface normal. Some of the H₂O adsorbed at 80 K on clean Al(111) can be desorbed in molecular form, but a considerable fraction dissociates upon heating into OH_ads and hydrogen, which leaves the surface as H₂. Following adsorption of H₂O onto oxygen-precovered Al(111), additional OH_ads is formed upon heating (perhaps via a hydrogen abstraction reaction), and H₂ desorbs at temperatures considerably higher than that seen for H₂O on clean Al(111). The general behavior of H₂O adsorption on clean and oxygen-precovered Al(111) (θ_O ? monolayer) is rather similar at low temperature, but much higher reactivity for dissociative adsorption of H₂O to form OH _adsis noted on the oxygen-dosed surface around room temperature.     

Intertwined electronic and structural phase transitions in the In/Si(111) interface

The structural (4 x 1) to (8 x 2) transition and the electronic metal to semimetal transition at the In/Si interface are studied with scanning tunneling microscopy and spectroscopy. Both transitions are gradual, resulting in a complex domain structure in the transition temperature regime. At these intermediate temperatures, the metallic (4 x 1) and semimetallic (8 x 2) domains coexist with each other and with new nanophases. By probing the two intertwined but distinguishable transitions at the atomic level, the interaction between different phases is visualized directly.     

The interaction of CO and O2 with the (111) surface of Pt3Ti

The electronic properties of clean and partly oxidized Pt₃Ti(111) surfaces have been studied utilizing carbon monoxide both as a probe and as a reducing agent. Vibrational frequencies and desorption profiles of chemisorbed CO as well as ion scattering and angular resolved X-ray photoelectron spectroscopy (XPS) suggest that the first atomic layer of annealed Pt₃Ti(111) is quasi-pure platinum. Scarcely any (θ ≈ 0.01) dissociation of CO was observed. Minor shifts of vibrational frequencies and desorption temperatures compared to Pt(111) and a p(2 × 2) “reconstruction” of the clean surface reveal some influence of the bulk. Auger spectroscopy, XPS, and ion scattering all show an increased titanium signal as a result of oxidation. Surface bound atomic oxygen gives a vibrational band around 650 cm⁻¹ which coincides with infrared absorption spectra of TiO₂. Flashing with CO shifts the band to 500 cm⁻¹. Correlated with this shift we observe (i) CO₂ desorption at a temperature well above that observed for Pt(111)/O, (ii) an altered Ti XPS signal, and (iii) a reduced oxygen concentration. Subsequently adsorbed CO molecules vibrate at the same frequencies as on the bare surface, give the same c(4 × 2) LEED pattern, and desorb at the same temperatures but with reduced intensity, in all proving that the surface oxide only acts as a site-blocker with respect to the metal surface. Our current understanding of these observations is that oxygen creates “islands of TiO₂”, segregated to the surface but with no electronic influence on remaining areas of the platinum enriched metal surface. The hexacoordinated Ti⁴⁺ ions on the surface of these islands are reduced by CO to pentacoordinated Ti³⁺ species. The vibrational shift, 650 to 500 cm⁻¹, can be understood by the dipole active bands of a triatomic O−Ti⁴⁺ −O vibrator compared to a diatomic Ti³⁺−O vibrator.     

Geometry and electronic band structure of surfaces: the case of Ge(111):Sn and C(111)

We present an ab initio study of two semiconductor surfaces, the α phase of Sn on Ge(111) and the cleavage surface of diamond. The theoretical tools used (density functional theory (DFT) and many-body perturbation theory) are discussed in detail, and the advantages and disadvantages of the two approaches are pointed out. We show that in the case of diamond it is essential to go beyond the DFT single-particle approach, and to introduce quasiparticle effects through the GW approximation. PACS 73.20.-r; 73.20.At; 71.15.Mb     

Mössbauer spectra on [Fe(H2O)6]K2(SO4)2 exhibit slow electronic relaxation

Mössbauer spectra on single crystals of [Fe(H₂O)₆]K₂(SO₄)₂ in fields from 1.5 T to 5 T at temperatures from 4.2 K to 20 K show considerable line broadenings up to 0.95 mm/s. This broadening strongly depends on the specific line in the spectrum, the temperature, and the strength and direction of the external field. It is shown that these phenomena are due to electronic relaxation rates that are some-what slower (≈10^?8 s) than the fast relaxation limit.     

Temperature dependence of Pt(111) surface relaxation

A careful investigation of the Pt(111) surface has been carried out, using the MeV heliumscattering technique. The anomalously large surface relaxation effect reported previously has been identified as an experimental artifact resulting from an unexpectedly large surface damage effect at low temperature. Optimum conditions have been established for minimizing the main experimental sources of error: background subtraction, radiation damage, and deviations from the Rutherford scattering law. Using these optimum conditions, a series of scattering measurements has been made over the temperature range 40–300 K. At all temperatures, we observe a significant anisotropy in the 〈111〉 angular scans, indicating an outward relaxation of the Pt(111) surface plane. By comparing this observed anisotropy with a set of Monte Carlo simulations, a value of 0.03 ? 0.01 Å (i.e. 1.3 ? 0.4%) is obtained for the surface relaxation. The temperature dependence of the surface peak also indicates that the enhanced vibrational amplitude of the surface atoms is not nearly as large as had been derived previously from high-temperature LEED studies.     

111In(111Cd) quadrupole interaction in the chalcogenide spinel CdCr2Se4

The¹¹¹Cd quadrupole coupling in the spinel CdCr₂Se₄ is investigated by TDPAC after different sample treatments. The experiments are consistent with Se vacancies causing the non-cubic probe environments and with the assumption that the majority of the¹¹¹In atoms are positioned at A-sites.     

NO dissociation on Cu(111) and Cu2O(111) surfaces: a density functional theory based study

NO dissociation on Cu(111) and Cu(2)O(111) surfaces is investigated using spin-polarized density functional theory. This is to verify the possibility of using Cu-based catalyst for NO dissociation which is the rate limiting step for the NO(x) reduction process. The dissociation of molecularly adsorbed NO on the surface is activated for both cases. However, from the reaction path of the NO-Cu(2)O(111) system, the calculated transition state lies below the reference energy which indicates the possibility of dissociation. For the NO-Cu(111) system, the reaction path shows that NO desorption is more likely to occur. The geometric and electronic structure of the Cu(2)O(111) surface indicates that the surface Cu atoms stabilize themselves with reference to the O atom in the subsurface. The interaction results in modification of the electronic structure of the surface Cu atoms of Cu(2)O(111) which greatly affects the adsorption and dissociation of NO. This phenomenon further explains the obtained differences in the dissociation pathways of NO on the surfaces.     

Ultrasonic relaxation in Na2Zr1.5Mg0.5 (PO4)3-Al2O3 composite

We present the ultrasonic attenuation dependent on Al₂O₃ concentration at 3 MHz as a function of temperature in Na₂Zr_1.5Mg_0.5(PO₄)₃-Al₂O₃ composite. From the ultrasonic relaxation spectra, we obtained an activation energy and a relaxation strength and then compared to the data obtained from an analysis of frequency-dependent resistivity. The background attenuation at 430 K was also estimated. Owing to these results, we explained an ionic mechanism. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994.