Oxygen vacancies versus fluorine at CeO2(111): a case of mistaken identity?

We propose a resolution to the puzzle presented by the surface defects observed with STM at the (111) surface facet of CeO 2 single crystals. In the seminal paper of Esch et al. [Science 309, 752 (2005)] they were identified with oxygen vacancies, but the observed behavior of these defects is inconsistent with the results of density functional theory (DFT) studies of oxygen vacancies in the literature. We resolve these inconsistencies via DFT calculations of the properties of both oxygen vacancies and fluorine impurities at CeO2(111), the latter having recently been shown to exist in high concentrations in single crystals from a widely used commercial source of such samples. We find that the simulated filled-state STM images of surface-layer oxygen vacancies and fluorine impurities are essentially identical, which would render problematic their experimental distinction by such images alone. However, we find that our theoretical results for the most stable location, mobility, and tendency to cluster, of fluorine impurities are consistent with experimental observations, in contrast to those for oxygen vacancies. Based on these results, we propose that the surface defects observed in STM experiments on CeO2 single crystals reported heretofore were not oxygen vacancies, but fluorine impurities. Since the similarity of the simulated STM images of the two defects is due primarily to the relative energies of the 2p states of oxygen and fluorine ions, this confusion might also occur for other oxides which have been either doped or contaminated with fluorine.

Increasing the equilibrium solubility of dopants in semiconductor multilayers and alloys.

We have theoretically studied the possibility to control the equilibrium solubility of dopants in semiconductor alloys, by strategic tuning of the alloy concentration. From the modeled cases of C(0) in Si(x)Ge(1-x), Zn(-) and Cd(-) in Ga(x)In(1-x)P it is seen that under certain conditions the dopant solubility can be orders of magnitude higher in an alloy or multilayer than in either of the elements of the alloy. This is found to be due to the solubility's strong dependence on the lattice constant for size mismatched dopants. The equilibrium doping concentration in alloys or multilayers could therefore be increased significantly. More specifically, Zn- in a Ga(x)In(1-x)P multilayer is found to have a maximum solubility for x = 0.9, which is 5 orders of magnitude larger than that of pure InP.

Tuning LDA+U for electron localization and structure at oxygen vacancies in ceria.

We examine the real space structure and the electronic structure (particularly Ce4f electron localization) of oxygen vacancies in CeO(2) (ceria) as a function of U in density functional theory studies with the rotationally invariant forms of the LDA+U and GGA+U functionals. The four nearest neighbor Ce ions always relax outwards, with those not carrying localized Ce4f charge moving furthest. Several quantification schemes show that the charge starts to become localized at U approximately 3 eV and that the degree of localization reaches a maximum at approximately 6 eV for LDA+U or at approximately 5.5 eV for GGA+U. For higher U it decreases rapidly as charge is transferred onto second neighbor O ions and beyond. The localization is never into atomic corelike states; at maximum localization about 80-90% of the Ce4f charge is located on the two nearest neighboring Ce ions. However, if we look at the total atomic charge we find that the two ions only make a net gain of (0.2-0.4)e each, so localization is actually very incomplete, with localization of Ce4f electrons coming at the expense of moving other electrons off the Ce ions. We have also revisited some properties of defect-free ceria and find that with LDA+U the crystal structure is actually best described with U=3-4 eV, while the experimental band structure is obtained with U=7-8 eV. (For GGA+U the lattice parameters worsen for U>0 eV, but the band structure is similar to LDA+U.) The best overall choice is U approximately 6 eV with LDA+U and approximately 5.5 eV for GGA+U, since the localization is most important, but a consistent choice for both CeO(2) and Ce(2)O(3), with and without vacancies, is hard to find.

Comparison of techniques for detection of domestic infestations with Triatoma infestans in Brazil.

The detection of infestations of Triatominae in houses in regions endemic for Chagas's disease is a criterion frequently used in the selection of areas, or of individual houses, for treatment in insecticide campaigns as well as in the evaluation of insecticide performance. Several different methods for detecting domestic infestations with Triatominae were compared: night capture, capture of five bugs with the aid of a flushing-out agent and use of card boxes of the Gómez-Núñez type. The flushing-out and Gómez-Núñez box methods were found to be equally sensitive, although each failed to detect some infestations which the other detected. The night capture method was slightly more sensitive but was found to be impractical for insecticide trials. Improvement to the flushing-out method, notably the introduction of a systematic search technique, made it much more sensitive than the Gómez-Núñez box method for heavily infested houses and for houses three months after insecticide treatment. Although the sensitivity of the Gómez-Núñez box method increases when the boxes are left in place for a long time, this also limits the value of the information obtained regarding the evaluation of insecticides. On the basis of the results presented, the flushing-out method using a systematic search of the house was found to be the most suitable sampling technique, but it is recognized that this method still has limitations.

Molluscicidal activity of trifenmorph in field trials.

Trifenmorph granules provided 100% control of Biomphalaria glabrata and B. tenagophila when applied at 2 kg of active ingredient per hectare, except at one site with a pH of 5.6 where the snail population was reduced by only 50%. Granulation was found to facilitate application by either hand or mistblower, and reduces the risk of infection to the spray team. Applied to canal margins the granules had a residual toxic effect.

Field tests of hexabutyldistannoxane (TBTO) in slow-release formulations against Biomphalaria spp.

Hexabutyldistannoxane (TBTO) in an asphalt base was found to retain molluscicidal activity for more than a year in the field. It was not deactivated by immersion in mud or by drying and exposure to the sun. Complete elimination of planorbid snails was achieved and maintained when repopulation pressure was sporadic, but control of a continuously entering population was not practicable. Fixing the product at the site is important, and a formulation in fragments of rubber that floated failed after 1-2 months. TBTO apparently acts cumulatively in snails, but is only initially toxic to aquatic insects and fish, which return to repopulate treated areas that remain snail-free.