Alina Vlad

X-ray investigation of subsurface interstitial oxygen at Nb/oxide interfaces

We have investigated the dissolution of a natural oxide layer on a Nb(110) surface upon heating, combining x-ray reflectivity, grazing incidence diffuse scattering, and core-level spectroscopy. The natural oxide reduces after heating to 145°C partially from Nb2O5 to NbO2, and an enrichment in subsurface interstitial oxygen by ∼70% in a depth of 100A is observed. After heating to 300°C, the oxide reduces to NbO and the surplus subsurface oxygen gets dissolved into the bulk. Our approach can be applied for further investigation of the effect of subsurface interstitial oxygen on the performance of niobium rf cavities.

Huge metastable axial strain in ultrathin heteroepitaxial vertically aligned nanowires

Strain engineering is a powerful tool to tailor the physical properties of materials coherently stacked in an epitaxial heterostructure. Such an approach, applied to the mature field of planar heteroepitaxy, has yielded a variety of new phenomena and devices. Recently, heteroepitaxial vertically aligned nanocomposites have emerged as alternatives to planar structures. Owing to the peculiar geometry of such nanoarchitectures, efficient strain control can be achieved, opening the way to novel functionalities. In this paper, we report a very large tensile axial strain in epitaxial transition metal nanowires embedded in an oxide matrix. We show that axial strains in excess of 1.5% can be sustained over a large thickness (a few hundred nanometers) in epitaxial nanowires having ultrasmall diameters (∼3–6 nm). The axial strain depends on the diameter of the nanowires, reflecting its epitaxial nature and the balance of interface and elastic energies. Furthermore, it is experimentally shown that such strain is metastable, in agreement with the calculations performed in the framework of the Frenkel-Kontorova model. The diameter dependence and metastability provide effective ways to control the strain, an appealing feature for the design of functional nanoarchitectures.

Correlation between stoichiometry and surface structure of the polar MgAl2O4(100) surface as a function of annealing temperature

The correlation between surface structure, stoichiometry and atomic occupancy of the polar MgAl2O4(100) surface has been studied with an interplay of noncontact atomic force microscopy, X-ray photoelectron spectroscopy and surface X-ray diffraction under ultrahigh vacuum conditions. The Al/Mg ratio is found to significantly increase as the surface is sputtered and annealed in oxygen at intermediate temperatures ranging from 1073-1273 K. The Al excess is explained by the observed surface structure, where the formation of nanometer-sized pits and elongated patches with Al terminated step edges contribute to stabilizing the structure by compensating surface polarity. Surface X-ray diffraction reveals a reduced occupancy in the top two surface layers for both Mg, Al, and O and, moreover, vacancies are preferably located in octahedral sites, indicating that Al and Mg ions interchange sites. The excess of Al and high concentration of octahedral vacancies, very interestingly, indicates that the top few surface layers of the MgAl2O4(100) adopts a surface structure similar to that of a spinel-like transition Al2O3 film. However, after annealing at a high temperature of 1473 K, the Al/Mg ratio restores to its initial value, the occupancy of all elements increases, and the surface transforms into a well-defined structure with large flat terraces and straight step edges, indicating a restoration of the surface stoichiometry. It is proposed that the tetrahedral vacancies at these high temperatures are filled by Mg from the bulk, due to the increased mobility at high annealing temperatures.

In situ x-ray study of the oxidation of a vicinal NiAl(6,7,1) surface

We present an in situ surface x-ray diffraction study of the clean, oxidized and subsequently annealed surfaces of regularly stepped NiAl(6,7,1). Our results show that the UHV stable, clean surface is not faceted and consists of a regular array of (1,1,0) terraces and (0,1,1) steps. The topmost Al and Ni atoms on the terraces exhibit a rippled relaxation while the step atoms are relaxed towards the bulk. Preferential Al oxidation at 540 K and 6×10−6 mbar O2 leads to the formation of a 5 A thin, disordered alumina layer and induces Al vacancies and Ni anti-sites in the Al-depleted interfacial region. The terrace-step structure of the clean surface is maintained, but strong inward relaxations of the interfacial atoms change the strain field around the steps. Massive (1,1,0) faceting with facets up to 50 times larger than the original terraces occurs after high-temperature annealing, during which the surface oxide develops a complex long-range ordering. These results can be understood by the change of interfacial strain, which removes the energy barrier for mass transport. In addition, unlike in the case of low-index (1,1,0) surfaces, we find the step-induced suppression of twin domain formation in the alumina film grown on NiAl(6,7,1). Our results show that the interplay between oxidation and strain can have dramatic effects on the morphology of vicinal surfaces.

Real time observation of ultrathin epitaxial oxide growth during alloy oxidation

We have studied the thermal oxidation of the intermetallic alloy CoGa in situ, in real time on the atomic scale, during the growth of an ultrathin, epitaxial Ga oxide layer. On the basis of an extended set of surface x-ray diffraction data, density functional theory calculations and core level spectroscopy data, we find that the oxide film consists of an oxygen ion double layer, which contains the basic building block of bulk β-Ga2O3. The oxide formation takes place via the nucleation of two-dimensional, anisotropic oxide islands which laterally grow and coalesce. A dramatic increase of the oxide island size is observed for low O2 pressures in the 10−8 mbar regime, which we interpret as the onset of a step flow like growth mode. This allows us to conclude that thermal oxidation can be considered as a hetero-epitaxial growth process, that follows similar atomistic growth principles to molecular beam epitaxy. As a consequence, the structural perfection of the oxide layer can be tailored by the appropriate choice of oxygen pressure and temperature.

In Situ Investigation of the Early-Stage Growth of Nanoporous Alumina

We report the successful use of in situ grazing incidence small-angle X-ray scattering to follow the anodization of aluminum. A dedicated electrochemical cell was designed and developed for this purpose with low X-ray absorption, with the possibility to access all azimuthal angles (360°) and to remotely control the temperature of the electrolyte. Three well-known fabrication techniques of nanoporous alumina, i.e., single, double, and pretextured, were investigated. The differences in the evolution of the scattering images are described and explained. From these measurements, we could determine at which moment the pores start growing even for very short anodization times. Furthermore, we could follow the thickness of the alumina layer as a function of the anodization time by monitoring the period of the Kiessig fringes. This work is aimed at helping to understand the different steps taking place during the anodization of aluminum at the very early stages of nanoporous alumina formation.