ABSTRACT
In the growing field of in operando and in situ X-ray experiments, there exists a large disparity in the types of environments and equipment to control them. This situation makes it challenging to conduct multiple experiments with a single mechanical interface to the diffractometer. Here, we describe the design and implementation of a modular instrument mounting system that can be installed on a standard six-circle diffractometer (e.g., 5021 Huber GmbH). This new system allows for the rapid changeover of different chambers and sample heaters and permits accurate sample positioning (x, y, z, and azimuthal rotation) without rigid coupling to the chamber body. Isolation of the sample motion from the chamber enclosure is accomplished through a combination of custom rotary seals and bellows. Control of the pressure and temperature has been demonstrated in the ranges of 10(-6)-10(3) Torr and 25°C-900°C, respectively. We have utilized the system with several different modular instruments. As an example, we provide in situ sputtering results, where the growth dynamics of epitaxial LaGaO3 thin films on (001) SrTiO3 substrates were investigated.
ABSTRACT
We present a synchrotron x-ray study of the equilibrium polarization structure of ultrathin PbTiO(3) films on SrRuO(3) electrodes epitaxially grown on SrTiO(3) (001) substrates, as a function of temperature and the external oxygen partial pressure (pO(2)) controlling their surface charge compensation. We find that the ferroelectric Curie temperature (T(C)) varies with pO(2) and has a minimum at the intermediate pO(2), where the polarization below T(C) changes sign. The experiments are in qualitative agreement with a model based on Landau theory that takes into account the interaction of the phase transition with the electrochemical equilibria for charged surface species. The paraelectric phase is stabilized at intermediate pO(2) when the concentrations of surface species are insufficient to compensate either polar orientation.
ABSTRACT
To study equilibrium changes in composition, valence, and electronic structure near the surface and into the bulk, we demonstrate the use of a new approach, total-reflection inelastic x-ray scattering, as a sub-keV spectroscopy capable of depth profiling chemical changes in thin films with nanometer resolution. By comparing data acquired under total x-ray reflection and penetrating conditions, we are able to separate the O K-edge spectra from a 10 nm La0.6Sr0.4CoO3 thin film from that of the underlying SrTiO3 substrate. With a smaller wavelength probe than comparable soft x-ray absorption measurements, we also describe the ability to easily access dipole-forbidden final states, using the dramatic evolution of the La N4,5 edge with momentum transfer as an example.
Subject(s)
Cobalt/chemistry , Lanthanum/chemistry , Oxides/chemistry , Strontium/chemistry , X-Ray Diffraction , Elasticity , Titanium/chemistryABSTRACT
New theoretical and experimental investigations of the occupied and unoccupied local electronic densities of states (DOS) are reported for alpha-Li(3)N. Band-structure and density-functional theory calculations confirm the absence of covalent bonding character. However, real-space full-multiple-scattering (RSFMS) calculations of the occupied local DOS find less extreme nominal valences than have previously been proposed. Nonresonant inelastic x-ray scattering, RSFMS calculations, and calculations based on the Bethe-Salpeter equation are used to characterize the unoccupied electronic final states local to both the Li and N sites. There is a good agreement between experiment and theory. Throughout the Li 1s near-edge region, both experiment and theory find strong similarities in the s-and p-type components of the unoccupied local final DOS projected onto an orbital angular momentum basis (l-DOS). An unexpected, significant correspondence exists between the near-edge spectra for the Li 1s and N 1s initial states. We argue that both spectra are sampling essentially the same final DOS due to the combination of long core-hole lifetimes, long photoelectron lifetimes, and the fact that orbital angular momentum is the same for all relevant initial states. Such considerations may be generally applicable for low atomic number compounds.
ABSTRACT
Non-resonant inelastic X-ray scattering of core electrons is a prominent tool for studying site-selective, i.e. momentum-transfer-dependent, shallow absorption edges of liquids and samples under extreme conditions. A bottleneck of the analysis of such spectra is the appropriate subtraction of the underlying background owing to valence and core electron excitations. This background exhibits a strong momentum-transfer dependence ranging from plasmon and particle-hole pair excitations to Compton scattering of core and valence electrons. In this work an algorithm to extract the absorption edges of interest from the superimposed background for a wide range of momentum transfers is presented and discussed for two examples, silicon and the compound silicondioxide.
