Andrei Ionut Mardare

Quantitative optical recognition of highly reproducible ultrathin oxide films in microelectrochemical anodization

Automatized microelectrochemical investigations are achieved using a scanning droplet cell. The area reproducibility for a 100 mum oxide spot is found to be better than 1%, a value typically difficult to reach even in macroscopic samples. A systematic change in color appearance is seen for oxide films with a thickness ranging from 14 to 27 nm. Analysis of optical images yields a strictly linear relation between relative transmission and anodization charge and thus allows determination of the oxide thickness with a remarkable precision better than 0.5 nm at an absolute film thickness value that is at least a factor of 20 smaller than the wavelength of light.

Combinatorial Electrochemistry on Al–Fe Alloys

Abstract Combinatorial material development was combined with high throughput microelectrochemistry to allow an efficient but comprehensive investigation of the interface chemistry of Al rich Al–Fe alloys as a function of their chemical composition. Composition spread thin films with a linear composition gradient were produced by thermal codeposition. A scanning droplet cell was used to determine the open circuit potential and to perform successive anodic oxide formation with intermittent impedance spectroscopy. The film formation factor, the relative permittivity of the oxides and the onset potential of oxide formation were determined quantitatively as function of the composition with a resolution of 0.5 at.%. An unexpected synergistic effect is found in a very narrow composition range between 9 and 12 at.% Fe. This effect, which shifts the onset potential by nearly 1 V, is discussed in terms of a local accumulation of Fe resulting in a redox stabilisation of space charge layer formation during high-field oxide growth. The results are supported by composition and depth dependent XPS measurements.

Photoelectrochemical Scanning Droplet Cell Microscopy (PE‐SDCM)

Principles of localised photoelectrochemistry are summarised and an experimental approach is described that allows the performance of the most important photoelectrochemical experiments within a diameter of 100 μm. Various light sources, such as a continuum emitter with a monochromator, LEDs, and lasers are coupled into a multi-mode fibre to illuminate a small spot that is wetted by the electrolyte from a capillary. Reference electrode, counter electrode, and optical fibre are installed in the capillary system. The performance of this system is demonstrated by photocurrent measurements on n-doped Si and p-doped Si as model substrates. A thickness-graded aluminium thin film for partial shadowing on Si proves the applicability for material library investigations in combinatorial materials science. Further experiments demonstrate the possibility of electrical light chopping as well as impedance spectroscopy with subsequent Mott-Schottky analysis for the determination of charge-carrier concentration and type, flat-band potential, and inversion layer formation. Photoelectrochemical scanning droplet cell microscopy (PE-SDCM) is an extremely versatile tool for the screening of water splitting photoelectrodes, the characterisation of photocatalysts, and high throughput characterisation of microgram amounts of new solar cell materials.

Localized photoelectrochemistry on a tungsten oxide-iron oxide thin film material library.

A WO3-Fe2O3 thin film combinatorial library was fabricated using a vapor phase co-deposition method followed by a combined thermal annealing and oxidation process. The scanning electron microscopy (SEM) analysis of the library microstructure combined with X-ray diffraction (XRD) investigations suggested that α-Fe2O3 grains preferentially grow from boundaries of domains, containing finer grains of WO3 and Fe2WO6, forming filiform networks on the surface. The surface density of the hematite networks depends on the amount of Fe present in the library. Photocurrents measured at different applied biases using Photo Electrochemical Scanning Droplet Cell Microscopy (PE-SDCM) were analyzed and mapped along the entire compositional spread. A distinctive photocurrent peak was detected at 21.9 atom % Fe, and its appearance was correlated to the higher amount of hematite present in the library at this specific composition together with a specific WO3 crystallographic orientation ((222) orthorhombic or (400) monoclinic). This finding is confirmed by qualitative and quantitative XPS surface analysis at the photocurrent peak position in the material library. Thus the enhancement of the photocurrent cannot be exclusively attributed to certain surface modifications since only hematite was found on the library surface at the peak composition.

Properties of anodic oxides grown on a hafnium–tantalum–titanium thin film library

Abstract A ternary thin film combinatorial materials library of the valve metal system Hf–Ta–Ti obtained by co-sputtering was studied. The microstructural and crystallographic analysis of the obtained compositions revealed a crystalline and textured surface, with the exception of compositions with Ta concentration above 48 at.% which are amorphous and show a flat surface. Electrochemical anodization of the composition spread thin films was used for analysing the growth of the mixed surface oxides. Oxide formation factors, obtained from the potentiodynamic anodization curves, as well as the dielectric constants and electrical resistances, obtained from electrochemical impedance spectroscopy, were mapped along two dimensions of the library using a scanning droplet cell microscope. The semiconducting properties of the anodic oxides were mapped using Mott–Schottky analysis. The degree of oxide mixing was analysed qualitatively using x-ray photoelectron spectroscopy depth profiling. A quantitative analysis of the surface oxides was performed and correlated to the as-deposited metal thin film compositions. In the concurrent transport of the three metal cations during oxide growth a clear speed order of Ti > Hf > Ta was proven.

Photoelectrochemical scanning droplet cell microscopy for localized photovoltaic investigations on organic semiconductors

Photoelectrochemical characterization of the regioregular poly(3-hexylthiophene) (P3HT) was performed using an adapted version of a photoelectrochemical scanning droplet cell microscope (PE-SDCM). The real and imaginary parts of the dielectric function were determined using spectroscopic ellipsometry in order to identify the absorption region of the polymer. Detailed photoelectrochemical experiments were performed for the thin polymer layer contacted with 0.1 M tetrabutylammonium hexafluorophosphate dissolved in propylene carbonate as well as with an electrolyte containing a 5.4 mM ferrocene/ferrocenium redox couple. The effect of the illumination on the P3HT covered WE in contact with both the pure electrolyte and an electrolyte containing a ferrocene/ferrocenium redox couple was studied using dark/illumination sequences. The stability of the photovoltaic effect was characterized using long term current transients. Finally, the photoelectrochemical impedance spectroscopy was applied to determine the electrical properties of the P3HT in the dark and under illumination.

Pulsed laser deposition of SiO2 - P2O5 - CaO - MgO glass coatings on titanium substrates

Thin films of bioactive glass-ceramic have been deposited on titanium substrates by the Pulsed Laser Deposition (PLD) technique under different experimental conditions. The effect of parameters such as deposition pressure and temperature of heat treatments was studied. The microstructure and the crystalline phases of the coatings were characterized using SEM, EDX and XRD analysis; the phases present were titanium oxides, calcium magnesium silicates and phosphates. The adhesion of the as-deposited films has been examined by scratch tests. The interfacial adhesion of the coatings was better when the deposition was performed at low pressure. Samples were immersed in simulated body fluid (SBF), and a calcium-phosphate precipitate was observed on the surface of less crystallized samples, suggesting that there is some relationship between surface reactivity and crystallinity.

Compositionally Dependent Nonlinear Optical Bandgap Behavior of Mixed Anodic Oxides in Niobium-Titanium System

Optical bandgap mapping of Nb-Ti mixed oxides anodically grown on a thin film parent metallic combinatorial library was performed via variable angle spectroscopic ellipsometry (VASE). A wide Nb-Ti compositional spread ranging from Nb-90 at.% Ti to Nb-15 at.% Ti deposited by cosputtering was used for this purpose. The Nb-Ti library was stepwise anodized at potentials up to 10 V SHE, and the anodic oxides optical properties were mapped along the Nb-Ti library with 2 at.% resolution. The surface dissimilarities along the Nb-Ti compositional gradient were minimized by tuning the deposition parameters, thus allowing a description of the mixed Nb-Ti oxides based on a single Tauc-Lorentz oscillator for data fitting. Mapping of the Nb-Ti oxides optical bandgap along the entire compositional spread showed a clear deviation from the linear model based on mixing individual Nb and Ti electronegativities proportional to their atomic fractions. This is attributed to the strong amorphization and an in-depth compositional gradient of the mixed oxides. A systematic optical bandgap decrease toward values as low as 2.0 eV was identified at approximately 50 at.% Nb. Mixing of Nb2O5 and TiO2 with both amorphous and crystalline phases is concluded, whereas the possibility of complex NbaTibOy oxide formation during anodization is unlikely.

Photoelectrochemical and Electrochemical Characterization of Sub- Micro-Gram Amounts of Organic Semiconductors Using Scanning Droplet Cell Microscopy

A model organic semiconductor (MDMO-PPV) was used for testing a modified version of a photoelectrochemical scanning droplet cell microscope (PE-SDCM) adapted for use with nonaqueous electrolytes and containing an optical fiber for localized illumination. The most attractive features of the PE-SDCM are represented by the possibility of addressing small areas on the investigated substrate and the need of small amounts of electrolyte. A very small amount (ng) of the material under study is sufficient for a complete electrochemical and photoelectrochemical characterization due to the scanning capability of the cell. The electrochemical behavior of the polymer was studied in detail using potentiostatic and potentiodynamic investigations as well as electrochemical impedance spectroscopy. Additionally, the photoelectrochemical properties were investigated under illumination conditions, and the photocurrents found were at least 3 orders of magnitude higher than the dark (background) current, revealing the usefulness of this compact microcell for photovoltaic characterizations.

Simple Method for Crystallizing Ceramic Thin Films Using Platinum Bottom Electrodes as Resistive Heating Elements

A simple method for crystallizing amorphous thin films was developed using platinum bottom electrodes as heating elements. A current was applied to chromel wires in contact with the platinum and the temperature was measured using a type K thermocouple. A proportional feedback algorithm was used for controlling the process. The optimum parameters for the temperature control were determined and applied to the crystallization of PZT thin films. The results obtained for a heat treatment at 650°C with a 15°C/s heating and cooling rate showed a pure perovskite phase; the ferroelectric properties were comparable with those from conventional heat treatment methods.