Cristian M. Teodorescu

An approximation of the Voigt I profile for the fitting of experimental X-ray absorption data

Abstract An analytical expression of the Voigt integral, derived by numerical methods, is proposed. It spans a wide range in X-ray spectral region in which the Lorentzian broadening of atomic origin and the Gaussian (instrumental) broadenings are of comparable magnitude. The indefinite integral of this expression is easy to evaluate and provide a good approximation for the X-ray threshold profiles. The proposed expressions are compared with previously proposed Voigt profiles and an example of experimental data analysis by fitting the lines and threshold profiles is given.

Surface versus volume effects in luminescent ceria nanocrystals synthesized by an oil-in-water microemulsion method

Pure and europium (Eu(3+)) doped cerium dioxide (CeO(2)) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of ~250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce(4+) sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 °C, a remarkable high surface area of ~120 m(2) g(-1) is preserved whereas an enrichment of the surface Ce(4+) relative to Ce(3+) ions and relative strong europium emission with a lifetime of ~1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.

Polarization-control of the potential barrier at the electrode interfaces in epitaxial ferroelectric thin films.

Electrode interface is a key element in controlling the macroscopic electrical properties of the ferroelectric capacitors based on thin films. In the case of epitaxial ferroelectrics, the electrode interface is essential in controlling the leakage current and the polarization switching, two important elements in the read/write processes of nonvolatile memories. However, the relation between the polarization bound charges and the electronic properties of the electrode interfaces is not yet well understood. Here we show that polarization charges are controlling the height of the potential barriers at the electrode interfaces in the case of Pb(Zr,Ti)O3 and BaTiO3 epitaxial films. The results suggest that the height is set to a value allowing rapid compensation of the depolarization field during the polarization switching, being almost independent of the metals used for electrodes. This general behavior open a new perspective in engineering interface properties and designing new devices based on epitaxial ferroelectrics.

Reducibility of ruthenium in relation with zeolite structure

Ru-zeolites prepared via deposition of aqueous solution of ruthenium chloride on X, L, ZSM-5 and APO-54 were investigated. The impregnated solids were characterized by the following techniques: N-2 sorption, H-2 chemisorption, TPR, XRD, XPS, EXAFS and Mossbauer spectroscopy. It was found that deposition of Ru is influenced by the pore structure and the chemical composition of the supports, in particular the concentration and strength of the protonic sites, with the formation of the different species. The packing of Ru as well as the degree of the reduction and the metal particle size are different according to the penetration depth of the metal and the nature of the zeolite. The amount of chlorine possibly remaining as adatoms of Ru is very low or inexistent. In calcined and reduced catalysts no chloride peak could be evidenced by XPS. The experiments confirmed that the use of large amounts of Ru chloride precursor leads to rather large metal particles

Structure of Fe layers grown on InAs(100)

We have studied the growth of Fe thin layers on In-terminated InAs(100) surfaces by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and reflection high energy electron diffraction (RHEED). Islanding is observed at the early stages of Fe deposition, then the growing mechanism is layer-by-layer. In thicker films, iron atoms are arranged in an unstrained bcc structure with a lattice constant close to that of bulk α-Fe. Arsenic diffuses through the Fe layer within a typical diffusion length of around 7 A. In turn, indium atoms remain at the interface.

S 2p excitation and fragmentation of sulfur aggregates

Synchrotron radiation from the storage ring BESSY-I is used to excite the S 2p regime (150–190 eV) of sulfur aggregates Sn, n=2–8. Valence states are identified in photoion yield spectra of mass selected Sn+ cations in combination with extended Huckel calculations. Mass spectra, partial ion yields, and photoelectron–photoion–photoion (PEPIPICO) coincidence spectra are reported, yielding a consistent picture of massive decay processes occurring in the S 2p regime. PEPIPICO spectra especially give detailed information on the fragmentation mechanisms of doubly charged aggregates. It is shown that most cation pairs are formed via charge separation originating from S8++. We derive values for the kinetic energy releases in multistep fragmentations assuming that charge separation is driven by Coulomb explosion.

Selective adsorption of contaminants on Pb(Zr,Ti)O3 surfaces shown by X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy (XPS) analyses of lead zirco-titanate Pb(Zr,Ti)O3(001) single crystal thin layers as a function of the time spent between sample preparation by pulsed laser deposition and introduction in to a ultrahigh vacuum revealed the fact that freshly prepared samples showed a shift of the C 1s towards a higher binding energy, together with shifts of core levels originating from the substrate (particularly Ti 2p and O 1s) towards a lower binding energy. This behaviour is explained by considering that the molecules of contaminants (fatty acids, alcohols, esters) are adsorbed preferentially on areas exhibiting outwards polarization P(+). Thus, photoelectrons originating from contaminants will have larger binding energies because of the charge state of the P(+) areas, whereas the substrate XPS signals from these P(+) areas are attenuated by the contaminants, with the consequence of a prevalence of XPS substrate signals originating from the P(−) areas, shifted towards lower binding energies. Piezoresponse force microscopy confirmed the assumptions derived from XPS results and suggests the existence of an interplay between the adsorption of contaminants and the surface polarization state.

Polarization induced self-doping in epitaxial Pb(Zr0.20Ti0.80)O3 thin films

The compensation of the depolarization field in ferroelectric layers requires the presence of a suitable amount of charges able to follow any variation of the ferroelectric polarization. These can be free carriers or charged defects located in the ferroelectric material or free carriers coming from the electrodes. Here we show that a self-doping phenomenon occurs in epitaxial, tetragonal ferroelectric films of Pb(Zr0.2Ti0.8)O3, consisting in generation of point defects (vacancies) acting as donors/acceptors. These are introducing free carriers that partly compensate the depolarization field occurring in the film. It is found that the concentration of the free carriers introduced by self-doping increases with decreasing the thickness of the ferroelectric layer, reaching values of the order of 1026 m−3 for 10 nm thick films. One the other hand, microscopic investigations show that, for thicknesses higher than 50 nm, the 2O/(Ti+Zr+Pb) atomic ratio increases with the thickness of the layers. These results suggest that the ratio between the oxygen and cation vacancies varies with the thickness of the layer in such a way that the net free carrier density is sufficient to efficiently compensate the depolarization field and to preserve the outward direction of the polarization.

Schottky barrier versus surface ferroelectric depolarization at Cu/Pb(Zr, Ti)O3 interfaces

The band bending at Cu/PZT(001) interfaces is investigated by X-ray photoelectron spectroscopy (XPS) for a PZT(001) layer which exhibits initial outwards ferroelectric polarization. Two competitive processes are identified: (a) formation of the Schottky barrier between the ferroelectric and unconnected Cu islands, and (b) coalescence of the Cu islands, realisation of an electrical contact to the ground of the system, inducing the apparent loss of the component of the ferroelectric polarization perpendicular to the sample surface, at least as it manifests in band bending. Three mechanisms are proposed to explain this loss of band bending when a full metal layer connected to ground is formed on the surface: (i) over-compensation of depolarization field in the sub-surface region, (ii) formation of domains with in-plane orientation of the polarization vector and (iii) loss of polarization in the near-surface layers of the ferroelectric due to electrons provided by the metal. These result in a non-monotonous variation of binding energies with the amount of Cu deposited. High resolution transmission electron microscopy and piezoresponse force microscopy confirmed these hypotheses. The XPS data allowed also to derive the surface PZT composition, its evolution with the deposition of copper and the formation of surface compounds.

Novel Pd heterogeneous catalysts for cycloisomerisation of acetylenic carboxylic acids

The Pd-TPPTS complex (TPPTS - trisodium salt of 3,3′,3′′-phosphanetriyl benzenesulfonic acid) and PdCl42− salt heterogenised onto Zn2AlNO3 layered double hydroxide (LDH) using an ion-exchange procedure, have been shown to be efficient green catalysts in the cycloisomerisation reaction of acetylenic carboxylic acids to the corresponding 5-membered heterocycles.