Raluca Negrea

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.

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.

Facile, high yield ultrasound mediated protocol for ZnO hierarchical structures synthesis: Formation mechanism, optical and photocatalytic properties

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV-Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface.

Co environment and magnetic defects in anatase CoxTi1−xO2 nanopowders

Cobalt environment and magnetic defects nature in hydrothermal synthesized anatase CoxTi1−xO2 nanopowders (0 ≤ x ≤ 0.1) are investigated by x-ray diffraction and a variety of spectroscopic techniques. One shows that cobalt is partially inserted in the anatase lattice, as Co2+ ions located on substitutional and interstitial sites. The fraction of the diluted Co is limited to 3 at. % for x ≥ 0.05, while the rest of the Co atoms gather into Co3O4 clusters. As found by electron paramagnetic resonance, the Co doping brings about hole- and electron-excess defects.

Electrical properties of single CuO nanowires for device fabrication: Diodes and field effect transistors

High aspect ratio CuO nanowires are synthesized by a simple and scalable method, thermal oxidation in air. The structural, morphological, optical, and electrical properties of the semiconducting nanowires were studied. Au-Ti/CuO nanowire and Pt/CuO nanowire electrical contacts were investigated. A dominant Schottky mechanism was evidenced in the Au-Ti/CuO nanowire junction and an ohmic behavior was observed for the Pt/CuO nanowire junction. The Pt/CuO nanowire/Pt structure allows the measurements of the intrinsic transport properties of the single CuO nanowires. It was found that an activation mechanism describes the behavior at higher temperatures, while a nearest neighbor hopping transport mechanism is characteristic at low temperatures. This was also confirmed by four-probe resistivity measurements on the single CuO nanowires. By changing the metal/semiconductor interface, devices such as Schottky diodes and field effect transistors based on single CuO p-type nanowire semiconductor channel are obtained. These devices are suitable for being used in various electronic circuits where their size related properties can be exploited.

High Permittivity (1 - x)Ba(Zr(0.2)Ti(0.8))O3 - x(Ba(0.7)Ca(0.3))TiO3 (x = 0.45) Epitaxial Thin Films with Nanoscale Phase Fluctuations.

Epitaxial (1 - x)Ba(Ti0.8Zr0.2)TiO3 - x(Ba0.7Ca0.3)TiO3, x = 0.45 (BCZT 45), thin films have been deposited on (001) SrTiO3 (STO) and (001/100) SrLaAlO4 (SLAO) substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscopy (HRTEM) confirmed the epitaxial growth of the films. A high structural quality has been evidenced for the BCZT/STO films. Geometric phase analysis (GPA) associated with the HRTEM enabled us to obtain microstrain analysis and the in-plane and out-of-plane lattice parameter variation on different areas. Tetragonality ratio fluctuations at nanoscale level which are relevant for the existence of nanodomains have been evidenced on the BCZT/STO films. The in-plane dielectric constant has been measured on interdigital electrodes deposited by lift-off technique on the top of the films. High values of dielectric permittivity (>3000) combined with low dielectric loss (<0.01) are obtained for BCZT 45 film deposited on STO substrate, showing nearly constant values between 1 kHz and 10 MHz. The high dielectric permittivity of BCZT thin films was attributed to their high structural quality and to the loss of rotation stability of the polarization associated with the presence of nanodomains. This results into a divergence of fluctuations of polarization direction and a peak of dielectric susceptibility. The enhanced switching of such nanodomain configuration was probed by piezoforce microscopy, by writing and reading domains during topography scanning.

Joining Chemical Pressure and Epitaxial Strain to Yield Y-doped BiFeO3 Thin Films with High Dielectric Response.

BiFeO3 is one of the most promising multiferroic materials but undergoes two major drawbacks: low dielectric susceptibility and high dielectric loss. Here we report high in-plane dielectric permittivity (ε’ ∼2500) and low dielectric loss (tan δ < 0.01) obtained on Bi0.95Y0.05FeO3 films epitaxially grown on SrTiO3 (001) by pulsed laser deposition. High resolution transmission electron microscopy and geometric phase analysis evidenced nanostripe domains with alternating compressive/tensile strain and slight lattice rotations. Nanoscale mixed phase/domain ensembles are commonly found in different complex materials with giant dielectric/electromechanical (ferroelectric/ relaxors) or magnetoresistance (manganites) response. Our work brings insight into the joined role of chemical pressure and epitaxial strain on the appearance of nanoscale stripe structure which creates conditions for easy reorientation and high dielectric response, and could be of more general relevance for the field of materials science where engineered materials with huge response to external stimuli are a highly priced target.

Ambiguous Role of Growth-Induced Defects on the Semiconductor-to-Metal Characteristics in Epitaxial VO2/TiO2 Thin Films

Controlling the semiconductor-to-metal transition temperature in epitaxial VO2 thin films remains an unresolved question both at the fundamental as well as the application level. Within the scope of this work, the effects of growth temperature on the structure, chemical composition, interface coherency and electrical characteristics of rutile VO2 epitaxial thin films grown on TiO2 substrates are investigated. It is hereby deduced that the transition temperature is lower than the bulk value of 340 K. However, it is found to approach this value as a function of increased growth temperature even though it is accompanied by a contraction along the V4+-V4+ bond direction, the crystallographic c-axis lattice parameter. Additionally, it is demonstrated that films grown at low substrate temperatures exhibit a relaxed state and a strongly reduced transition temperature. It is suggested that, besides thermal and epitaxial strain, growth-induced defects may strongly affect the electronic phase transition. The results of this work reveal the difficulty in extracting the intrinsic material response to strain, when the exact contribution of all strain sources cannot be effectively determined. The findings also bear implications on the limitations in obtaining the recently predicted novel semi-Dirac point phase in VO2/TiO2 multilayer structures.

On the threshold for ion track formation in CaF2

There is ongoing debate regarding the mechanism of swift heavy ion track formation in CaF2. The objective of this study is to shed light on this important topic using a range of complimentary experimental techniques. Evidence of the threshold for ion track formation being below 3 keV/nm is provided by both transmission electron microscopy and Rutherford backscattering spectroscopy in the channeling mode which has direct consequences for the validity of models describing the response of CaF2 to swift heavy ion irradiation. Advances in the TEM and RBS/c analyses presented here pave the way for better understanding of the ion track formation.