Stela Canulescu

Mechanisms of the laser plume expansion during the ablation of LiMn2O4

Films of LiMn2O4 prepared by pulsed laser ablation deposition are typically lithium deficient when grown at background pressures ranging between 10−4 and 20 Pa. The deficiency of light atomic species such as lithium in LiMn2O4 thin films occurs as a result of the different behavior of the species during plume expansion and the deposition of the film at elevated deposition temperatures. The plasma plume evolution in vacuum and 20 Pa oxygen pressure are studied using two spectroscopic techniques: emission spectroscopy and plume imaging. Higher velocities and a wider spatial distribution of lithium atoms are observed in vacuum when compared with manganese and oxygen species. Plume species are slowed down due to collisions with gas molecules when ablating LiMn2O4 in an oxygen atmosphere. As a result, a strong deceleration of the plasma front occurs, and the effect is more pronounced for the light species, e.g., Li. Comparing the spatial manganese and lithium distribution within the plasma, the lithium species...

Pulsed radiofrequency glow discharge time-of-flight mass spectrometry for molecular depth profiling of polymer-based films

We demonstrate the potential of an innovative technique, pulsed radiofrequency glow discharge time-of-flight mass spectrometry, for the molecular depth profiling of polymer materials. The technique benefits from the presence, in the afterglow of the pulsed glow discharge, of fragment ions that can be related to the structures of the polymers under study. Thin films of different polymers (PMMA, PET, PAMS, PS) were successfully profiled with retention of molecular information along the profile. Multilayered structures of the above polymers were also profiled, and it was possible to discriminate among layers having similar elemental composition but different polymer structure.

Potential analytical applications of negative ions from a pulsed radiofrequency glow discharge in argon

Detection of negative ions from a conventional analytical glow discharge source using argon as the working gas is reported. The negative ions are recorded using a pulsed discharge source coupled with a time-of-flight mass spectrometer. A considerable enhancement in the “afterglow” region of the negative ion signal for halogens and halogenated molecules and reduction in background is observed. This is the first time when negative ions have been reported for halogen containing materials and we illustrate our findings with results from the polytetrafluoroethene polymer (PTFE).

Pulsed laser deposition from ZnS and Cu2SnS3 multicomponent targets

Abstract Thin films of ZnS and Cu 2 SnS 3 have been produced by pulsed laser deposition (PLD), the latter for the first time. The effect of fluence and deposition temperature on the structure and the transmission spectrum as well as the deposition rate has been investigated, as has the stoichiometry of the films transferred from target to substrate. Elemental analysis by energy dispersive X-ray spectroscopy indicates lower S and Sn content in Cu 2 SnS 3 films produced at higher fluence, whereas this trend is not seen in ZnS. The deposition rate of the compound materials measured in atoms per pulse is considerably larger than that of the individual metals, Zn, Cu, and Sn.

Band gap structure modification of amorphous anodic Al oxide film by Ti-alloying

The band structure of pure and Ti-alloyed anodic aluminum oxide has been examined as a function of Ti concentration varying from 2 to 20 at. %. The band gap energy of Ti-alloyed anodic Al oxide decreases with increasing Ti concentration. X-ray absorption spectroscopy reveals that Ti atoms are not located in a TiO2 unit in the oxide layer, but rather in a mixed Ti-Al oxide layer. The optical band gap energy of the anodic oxide layers was determined by vacuum ultraviolet spectroscopy in the energy range from 4.1 to 9.2 eV (300–135 nm). The results indicate that amorphous anodic Al2O3 has a direct band gap of 7.3 eV, which is about ∼1.4 eV lower than its crystalline counterpart (single-crystal Al2O3). Upon Ti-alloying, extra bands appear within the band gap of amorphous Al2O3, mainly caused by Ti 3d orbitals localized at the Ti site.

Detection of negative ions in glow discharge mass spectrometry for analysis of solid specimens.

A new method is presented for elemental and molecular analysis of halogen-containing samples by glow discharge time-of-flight mass spectrometry, consisting of detection of negative ions from a pulsed RF glow discharge in argon. Analyte signals are mainly extracted from the afterglow regime of the discharge, where the cross section for electron attachment increases. The formation of negative ions from sputtering of metals and metal oxides is compared with that for positive ions. It is shown that the negative ion signals of F− and TaO2F− are enhanced relative to positive ion signals and can be used to study the distribution of a tantalum fluoride layer within the anodized tantala layer. Further, comparison is made with data obtained using glow-discharge optical emission spectroscopy, where elemental fluorine can only be detected using a neon plasma. The ionization mechanisms responsible for the formation of negative ions in glow discharge time-of-flight mass spectrometry are briefly discussed.

Structure, microstructure, and high-temperature transport properties of La1−xCaxMnO3−δ thin films and polycrystalline bulk materials

Single-phase samples of La1−xCaxMnO3−δ (LCMO), x≈0.3, prepared by pulsed reactive crossed beam laser ablation on SrTiO3 (STO) substrates, and soft chemistry synthesized powders were studied by various methods. The precise study of the crystal structure and microstructures by a combination of electron diffraction and high-resolution electron microscopy revealed a monoclinic distortion of the GdFeO3-type structure, P21/c space group, in both types of materials, i.e., the thin films and powder compound. The analysis of the LCMO/STO interface showed nonhomogeneous stress states and a composition that results in a different superstructure from the usual detected structure. The temperature-dependent thermoelectric power in the case of thin films presented an anomalous behavior compared to those from the powder compound. A structural transition at high temperature (T≈750 K) influences the thermopower behavior as well as the thermal conductivity values.

Interfacial Structure and Photocatalytic Activity of Magnetron Sputtered TiO2 on Conducting Metal Substrates

The photocatalytic behavior of magnetron sputtered anatase TiO2 coatings on copper, nickel, and gold was investigated with the aim of understanding the effect of the metallic substrate and coating-substrate interface structure. Stoichiometry and nanoscale structure of the coating were investigated using X-ray diffraction, Raman spectroscopy, atomic force microscope, and scanning and transmission electron microscopy. Photocatalytic behavior of the coating was explored by using optical spectrophotometry and electrochemical methods via photovoltage, photocurrent, and scanning kelvin probe microscopy measurements. The nature of the metal substrate and coating-substrate interface had profound influence on the photocatalytic behavior. Less photon energy was required for TiO2 excitation on a nickel substrate, whereas TiO2 coating on copper showed a higher band gap attributed to quantum confinement. However, the TiO2 coating on gold exhibited behavior typical of facile transfer of electrons to and from the CB, therefore requiring only a small amount of photon energy to make the TiO2 coating conductive.

Nanoscale surface potential imaging of the photocatalytic TiO2 films on aluminum

The change in the surface potential of TiO2 coatings upon UV-illumination was investigated on the nanoscale using Scanning Kelvin Probe Force microscopy and on the micro-scale using photo-electrochemical measurements. A good correlation between the two techniques was obtained. The changes in the surface potential of TiO2 coatings upon UV-illumination are closely correlated to the band gap and thickness of the coatings. The inhomogeneity surface potential distribution of a 100 nm TiO2 film indicates a heterogeneous coating. Transition to a homogeneous surface potential distribution was observed with increasing thickness of the TiO2 coating.

A study on matrix assisted pulsed evaporation (MAPLE) of organic materials

Organic films can be produced either by MAPLE or directly by PLD (Pulsed laser deposition). For a reasonable deposition rate of ng/cm2 per pulse for film production by MAPLE a fluence of 1-1.5 J/cm2 is required at the laser wavelength of 355 nm, while the fluence can be considerably lower at 248 nm. At high fluence the deposition rate of proteins by MAPLE seems to decrease. The surface roughness is still an issue, but at low fluence it seems to be acceptable. The fragmentation rate increases with fluence, and seems to be less pronounced for MAPLE than for PLD. Also this issue is not yet resolved.