Dr. Viorica STANCU

Photoanodes based Ce-doped ZnO nanorods arrays were prepared by hydrothermal method in order to improve photoelectrochemical efficiency of ZnO photoanodes in water splitting process. Scanning electron microscopy investigation showed ZnO based nanorods with length of around 500 nm and different thicknesses and growth directions. Some morphological changes were noted following the thermal treatment. Energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy measurements proved the presence of cerium species both in bulk and on the surface of ZnO nanorods. A current density of 2.44 mA/cm(2) at 1.23 V against the reversible hydrogen electrode (0.265 V vs. Ag/AgCl) was obtained for Ce-doped ZnO sample, which is >162% increase over that of ZnO sample. The increased photocurrent value obtained for this sample was correlated with the passivation of surface defects evidenced by photoluminescence study and the increased concentration of Ce3+ on the surface. Also, the electrochemical impedance spectroscopy measurements suggested that Ce doping improves the charge transfer in bulk.

This study presents a systematic approach to engineering the electron transport layer (ETL) in perovskite solar cells using a spray deposition technique to fabricate sequentially compact and mesoporous titanium dioxide (c-TiO2, m-TiO2) films. The spray coating method leads to the development of a distinct reticulated morphology characterized by well-defined wavy-like surface features and significantly increased roughness-at least twice that of spin-coated mesoporous films. The increased interfacial area between the mesoporous TiO2 and the perovskite layer facilitates more efficient charge transfer, contributing to higher device performance. By optimizing the deposition parameters, particularly the number of spray cycles for the m-TiO2 layer, we achieve a significant enhancement in device performance, with improvements in power conversion efficiency (PCE), reduced series resistance, and minimized hysteresis. Our results demonstrate that an optimal film thickness promotes better perovskite anchoring, while excessive deposition impedes light transmission and increases sheet resistance. These findings advance the practical fabrication of high-performance perovskite solar cells using simple solution-processing techniques and highlights the potential of scalable spray deposition methods for industrial-scale fabrication.

Replacing lead atoms in halide perovskite materials is of significant importance for the development of environmentally friendly perovskite solar cells. In this paper, we investigated the effect of doping the MAPbI(2.6)Cl(0.4) hybrid perovskite (MA-methyl ammonium) with non-toxic elements, such as alkaline earth metal ions (Mg2+) and transition metal ions (Zn2+). The structural, morphological, and optical properties of the prepared samples were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis. spectroscopy. Finally, the doped films were used as photoactive layers in solar devices in order to evaluate their photovoltaic performance. Zn proved to be more appropriate to replace partially Pb and films with higher quality were obtained. As a result, the MAPb1(-x)Zn(x)I(2.6)Cl(0.4) based solar cells have demonstrated a slight improvement of the photovoltaic performances, resulting in a uniform and narrower PCEs (power conversion efficiency) range, compared to pristine MAPbI(2.6)Cl(0.4) based devices.

The technology of perovskite solar cells (PSC) is getting close to breaching the consumer market. Yet, one of the current challenges is to reduce the toxicity during their fabrication by reducing the use of the toxic solvents involved in the perovskite fabrication process. A good solubilization of lead halides used in hybrid perovskite preparation is required, and it is only possible with polar solvents. A mixture of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is the most popular solvent combination for a perovskite precursor solution. DMF is necessary to ensure a good dissolution of lead iodide, but it is also the most toxic solvent. In this paper, we study the replacement of the dimethylformamide with presumably less toxic alternatives, such as N-methyl-2-Pyrrolidone (NMP) and ethyl acetate (EA), for the preparation of the K(0.1)FA(0.7)MA(0.2)PbI(2.8)Cl(0.2) (KFAMA) hybrid perovskite. The perovskite thin films were investigated by various characterization techniques: X-ray diffraction, atomic force microscopy, scanning electron microscopy, and UV-vis spectroscopy, while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The present study shows that by keeping the same deposition parameters as when only DMF solvent is used, the partial solvent substitution with NMP and EA gives promising results for reducing the toxicity of the fabrication process of KFAMA-based PSCs. Thus, with no specific optimization of the deposition process, and for the maximum possible partial substitution of DMF with NMP and EA solvents, the loss in the power conversion efficiency (PCE) value is only 35% and 18%, respectively, associated with the more structural defects promoted by NMP and EA.

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.

Cu2NiSnS4 (CNTS) absorber layers are elaborated by electrodeposition at various applied potentials followed by sulfurization treatment at 450 degrees C under sulfur atmosphere. The microstructural investigations revealed the presence of Cu4SnS4 secondary phases which can be reduced using an applied potential of -1.15 V vs. Ag/AgCl. Using the corresponding cathodic potential for Ni2+, the competing detrimental hydrogen evolution regresses the morphology and composition. The film with the highest Ni concentration has a band gap of 1.44 eV as inferred from diffuse reflectance data. The Randles cell model is probed by electrochemical impedance spectroscopy.

Organic-inorganic hybrid perovskite solar cells are within the emerging photovoltaic technologies. The combination of different halogen ions, in certain fill fractions, is one of the methods to improve the perovskite film properties. Herein, fabrication and characterization of perovskite cells in standard mesoscopic architecture using one-step deposition method has been done. The role of the halogen ions (Chlorine or Bromine) on crystal structure growth and photoelectric performance has been investigated. X-ray diffraction, scanning electron microscopy, atomic force microscopy and optical microscopy analysis were performed. The microstructure, composition and morphology of CH3NH3PbI1.8Br1.2 and CH3NH3PbI1.8Cl1.2 films are dissimilar, although identical fabrication method was used. Same holds for optical properties, band gap energies of 1.84 eV and 1.63 eV, respectively, being obtained. Integrated in solar cells, the maximum power conversion efficiency of the Br based devices is beyond 10%, while for those based on Cl, the efficiency drops around 5%.

Fe (acceptor) and Nb (donor) doped epitaxial Pb(Zr0.2Ti0.8)O-3 (PZT) films were grown on single crystal SrTiO3 substrates and their electric properties were compared to those of un-doped PZT layers deposited in similar conditions. All the films were grown from targets produced from high purity precursor oxides and the doping was in the limit of 1% atomic in both cases. The remnant polarization, the coercive field and the potential barriers at electrode interfaces are different, with lowest values for Fe doping and highest values for Nb doping, with un-doped PZT in between. The dielectric constant is larger in the doped films, while the effective density of charge carriers is of the same order of magnitude. An interesting result was obtained from piezoelectric force microscopy (PFM) investigations. It was found that the as-grown Nb-doped PZT has polarization orientated upward, while the Fe-doped PZT has polarization oriented mostly downward. This difference is explained by the change in the conduction type, thus in the sign of the carriers involved in the compensation of the depolarization field during the growth. In the Nb-doped film the majority carriers are electrons, which tend to accumulate to the growing surface, leaving positively charged ions at the interface with the bottom SrRuO3 electrode, thus favouring an upward orientation of polarization. For Fe-doped film the dominant carriers are holes, thus the sign of charges is opposite at the growing surface and the bottom electrode interface, favouring downward orientation of polarization. These findings open the way to obtain p-n ferroelectric homojunctions and suggest that PFM can be used to identify the type of conduction in PZT upon the dominant direction of polarization in the as-grown films.

In the present work, stannite Cu2CoSnS4 (CCTS) films were elaborated using spray pyrolysis method on soda-lime glass, at different deposition temperatures (T-d = 250, 300, and 350 degrees C), followed by different chosen sulfurization temperatures (T-s = 450, 500, and 550 degrees C). X-ray diffraction (XRD) revealed the nearly single-phase formation of CCTS films at 300 degrees C deposition temperature. After sulfurization in argon flow, the XRD lines become narrower, the average crystallite size expanding above 70 nm. The Raman spectroscopy analysis confirmed the stannite structure formation, as well as the presence CoS2 secondary phases, which reduces at higher sulfurization temperature (550 degrees C). The energy dispersive spectroscopy results indicated atomic ratios of Cu/Co/Sn/S close to the ideal stoichiometric ratio 2:1:1:4. The room temperature photoluminescence emission is recorded with maximum in the 1.35-1.40 eV range. Thermoelectric properties are measured up to 130 degrees C, the films show poor power factor as a result of small positive Seebeck coefficients 10-45 Of K -1 and low electrical conductivity despite of having relatively high carrier concentration (similar to 10(20) cm(-3)).

In this study, stannite, Cu2FeSnS4 (CFTS), absorber films were obtained by electrodeposition on Molybdenum-coated soda-lime substrates, followed by sulfurization treatment at certain temperatures in the 400-550 degrees C range. The purposes of this work were to control the manufacturing of CFTS films with good stoichiometry, high crystallinity and to study the annealing temperature impact on CFTS films properties. The X-ray diffraction and the Raman spectroscopy measurement distinguished the CFTS phase formation, with a presence of SnS2 secondary phase. The energy dispersive spectroscopy results reveal compositional differences between samples as well as the in-depth gradients. The photoluminescence emission band around 1.35-1.40 eV is slightly below the direct bandgap inferred from the conventional spectroscopy (diffuse reflectance). X-ray photoelectron spectroscopy results indicate clearly a high amount of Sn on the surface. The Conversion Electron Mossbauer unveiled the presence of Fe in the chalcogenide unit cell. The electrochemical characteristics of the synthesized films are also given. (c) 2022 Elsevier B.V. All rights reserved.

In this paper, potassium based triple cation mixed-halide perovskite films were explored in order to enhance the stability and photovoltaic performance of perovskite based solar cells. It was found that adding potassium (K+) to a double cation mixed halide perovskite (FA(0.80)MA(0.20)PbI(2.8)Cl(0.2)), structural, morphological and optoelectronic properties of perovskites are improved. The perovskite films were prepared by one-step spin coating method with and without K+ and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The results indicate that potassium incorporation reduces significantly the yellow non-perovskite delta-phase formation and improves the perovskite film quality, thus contributing to the reduction of hysteresis, improves the stability and increases the PCE up to 12.51%. Furthermore, the doped devices exhibit reduced hysteresis and provide remarkable shelf stability by retaining more than 70% of the initial efficiency with low humidity over 850 h. (C) 2020 Elsevier B.V. All rights reserved.

Polarization switching in ferroelectric films is exploited in many applications, such as non-volatile memories and negative capacitance field affect transistors. This can be inhomogeneous or homogeneous, depending on if ferroelectric domains are forming or not during the switching process. The relation between the polarization switching, the structural quality of the films and the negative capacitance was not studied in depth. Here, Pb(Zr0.2Ti0.8)O-3 (PZT) layers were deposited by pulse laser deposition (PLD) and sol-gel (SG) on single crystal SrTiO3 (STO) and Si substrates, respectively. The structural quality was analyzed by X-ray diffraction and transmission electron microscopy, while the electric properties were investigated by performing hysteresis, dynamic dielectric measurements, and piezo-electric force microscopy analysis. It was found that the PZT layers grown by PLD on SRO/STO substrates are epitaxial while the layers deposited by SG on Pt/Si are polycrystalline. The polarization value decreases as the structure changes from epitaxial to polycrystalline, as well as the magnitude of the leakage current and of the differential negative capacitance, while the switching changes from homogeneous to inhomogeneous. The results are explained by the compensation rate of the depolarization field during the switching process, which is much faster in epitaxial films than in polycrystalline ones.

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.

Composites of BaTiO3 (BT) and doped-PZT (d-PZT) micro-particles randomly dispersed in a PDMS matrix were prepared by a molding process. The morpho-structural characterization, performed by SEM and XRD, showed ceramic micro-grains of cubic BT and orthorhombic d-PZT, randomly dispersed in the PDMS matrix. Polarization (P) as a function of the applied field (E) was measured for composite samples, as well as for polymer samples. Hysteresis loops typical for a dielectric material were obtained, but also atypical ones, especially for higher fraction of polymer in composite, lower fields and shorter measuring periods, as a result of the dielectric relaxation in polymer and the presence of interfacial polarization charges at the contact between polymer and ferroelectric. All these composites show very low polarizations (less than 0.2 mu C/cm(2) and 0.05 mu C/cm(2) the maximum and remnant polarization, respectively), caused by the very low dielectric constant of the polymer (less than 10), which drastically reduces, up to 100 times, the electric field effectively applied to the ferroelectric. Weak pyroelectric response was recorded on BT/PDMS, but a typical behavior of a pyroelectric detector was observed. A figure of merit of the material which exceeds 10(-4) m(2) /C was estimated.

Composites of magnetite (Fe3O4) nanoparticles dispersed in a polydimethylsiloxane (PDMS) matrix were prepared by a molding process. Two types of samples were obtained by free polymerization with randomly dispersed particles and by polymerization in an applied magnetic field. The magnetite nanoparticles were obtained from magnetic micrograins of acicular goethite (alpha-FeOOH) and spherical hematite (alpha-Fe2O3), as demonstrated by XRD measurements. The evaluation of morphological and compositional properties of the PDMS:Fe3O4 composites, performed by SEM and EDX, showed that the magnetic particles were uniformly distributed in the polymer matrix. Addition of magnetic dispersions promotes an increase of thermal conductivity compared with pristine PDMS, while further orienting the powders in a magnetic field during the polymerization process induces a decrease of the thermal conductivity compared with the un-oriented samples. The shape of the magnetic dispersions is an important factor, acicular dispersions providing a higher value for thermal conductivity compared with classic commercial powders with almost spherical shapes.

Hybrid perovskites based solar cells have demonstrated high conversion efficiency but poor long-term stability. This study reports on the results obtained after doping the CH3NH3PbI2.6Cl0.4 mixed halide perovskite with imidazolium (C3N2H5+, denoted IM) on the "A site" position of a perovskite, to improve photovoltaic performances and stability of hybrid perovskite solar cells. The perovskite films were investigated exhaustively by different characterization techniques: X-ray diffraction, Atomic Force Microscopy, Scanning Electron Microscopy, UV-Vis, X-ray Photoelectron Electron Paramagnetic Resonance spectroscopies, Impedance Spectroscopy and Incident Photon-to-Electron Conversion Efficiency. The photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The amount of IM inserted in the perovskite play a key role on the film properties. The calculated new tolerance factors according to the "globularity factor" are experimentally proved and thus at doping concentrations greater than 20% for CH3NH3PbI2.6Cl0.4 perovskite the 3D structure is no longer obtained. However, below this value, the IM substituted perovskite film possesses an improved film quality and crystallinity as compared to the pristine film. Substituting MA+ with IM+ provides a favorable way to reduce recombination processes and shows great potential to achieve high stability, and an improved charge generation, resulting in increased PCE values. We find that the optimal percentage of imidazolium incorporation to achieve better stability of solar cells is 6%.

We explore the cross coupling between the ferroelectric and ferromagnetic phases in Ni/BaTiO3(001) heterostructures and demonstrate the modulation of the magnetism and incidence of exchange bias in the ultrathin metallic Ni overlayer, depending on the ferroelectric state of the bottom layer. We establish that 5-nm-thick monocrystalline Ni film deposited on BaTiO3 with ferroelectric polarization pointing towards the surface (P+) favors the organization of Ni into uniform ferromagnetic domains. Ni grown on BaTiO3 with opposite ferroelectric polarization is featured by emerging exchange-bias coupling between the ferromagnetic Ni top layers and the antiferromagnetic reacted interface, as theoretically explained by first-principles calculations. We explicitly obtain the morphology of the magnetic domains of the crystalline Ni layer in atomic and magnetic force microscopy measurements (AFM/MFM). The resemblance of AFM and MFM images indicate that, although with radically different morphologies, in both cases all spins orient in the Ni plane. Consequently, the distinct signature of the ferroelectric-ferromagnetic coupling extracted from the magneto-optical Kerr effect measurements encodes all the information of sample magnetism. The peculiar magnetic coupling depending on the ferroelectric state indicates new ways of engineering the functionality of metal/ferroelectric interfaces.

The pyroelectric coefficient of some Pb(Zr,Ti)O-3 type ceramics was estimated using two methods: a direct method, based on the temperature dependence of the charge/current generated by pyroelectric effect; an indirect method based on the frequency dependence of the pyroelectric signal generated by a pyroelectric element under modulated irradiation with infrared light. The purpose was to compare the results and to assess if the indirect method is enough accurate for rapid estimation of the pyroelectric coefficient of a material envisaged for infrared detection. The direct method is more accurate and requires accurate control of temperature and heating rate, while the indirect method is less accurate, with an error up to 20%, and requires the knowledge of quantities such as dielectric constant, electric conductance, and incident power. However, the indirect method can be more easily implemented and can provide a rapid assessment on the pyroelectric quality of a material with potential use in infrared detectors.

Pb0.98Bi0.02Zr0.5Fe0.1Nb0.09Ti0.31O3 (PBiZFNT) powder obtained by a solid state reaction technique was uniaxial pressed and sintered at 1200 degrees C in order to fabricate dense thin disk ceramics with different thickness (200 mu up to 600 mu m). The pyroelectric response was influenced by the thickness of the ceramics. The thin ceramic disks of 250 mu m thickness show better pyroelectric signal (approximate to 35 mV) which recommend them for potential use in laser energy meters.

This study reports on the results obtained after doping the [CH3NH3](0.94)[C3N2H5](0.06)PbI2.6Cl0.4 mixt halide perovskite with europium or antimony (Eu3+/Sb3+) at the 'B site'. This way two new complex compounds were obtained, [CH3NH3](0.94)[C3N2H5](0.06)Pb1-yByI2.6Cl0.4 (B = Eu or Sb and y = 0-0.05) as perovskite precursor solutions and deposited as thin films. The properties of the perovskite films were investigated by various characterization techniques: x-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-vis spectroscopy while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. We find that doping the mixt halide perovskite with very small quantities of Sb improves the quality of the perovskite films and further improves the stability of perovskite solar cells.

In this work, the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 (MAPbI(3)) was studied, aiming to improve the properties of perovskite films used in solar cells application. The surface morphology, the microstructure and the optical properties of the obtained films containing different Europium (Eu) concentrations were characterized by atomic force microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, UV-vis spectroscopy and photoluminescence spectroscopy.

Temperature dependent interfacial coupling mechanisms in SRO/BFO/Fe layered structures were investigated. The BFO/Fe heterostructures were prepared by PLD and sputtering, respectively, on the STO(0 0 1) substrate with a 20 nm SRO buffer layer. An annealing treatment in external magnetic field was further applied. Complex characterizations with X-ray diffraction, atomic force microscopy, Transmission Electron Microscopy, Mossbauer spectroscopy, magneto-optic Kerr effect and SQUID magnetometry were performed. Before annealing, the films show good crystallization and epitaxy of the SRO and BFO layers with smooth interfaces. Two coupling mechanisms of the ferromagnetic layers (top Fe and bottom SRO, respectively) to the epitaxial BFO film with mainly antiferromagnetic structure were evidenced in the as deposited samples at low temperatures. Negative exchange bias fields of up to 67(10) Oe and 37(5) Oe at low temperatures were observed for the two ferromagnetic components, respectively, depending on the thickness of the Fe layer. The field annealing treatments induce a specific morphology and magnetic spin structure at both interfaces of the BFO spacer layer, giving rise to a long range magnetostatic coupling between the two ferromagnetic films, in addition to the interfacial couplings. Moreover, the experimentally evidenced Fe clusters penetrating the BFO/Fe interface toward the BFO layer give support for this interaction. As an additional consequence, a considerable enhancement of both uniaxial and unidirectional anisotropies as well as an increased blocking temperature of exchange bias were obtained. The involved exchange coupling mechanisms were discussed in detail. (C) 2018 Elsevier B.V. All rights reserved.

Ba0.75Sr0.25TiO3 (BST) and PbZr0.68Fe0.14Nb0.14Ti0.04O3 (PZFNT) ceramic pellets were obtained by ceramic technology and their structural, ferroelectric and pyroelectric properties were investigated. The relative density of BST and PZFNT is about 93% and 90%, respectively, with an average grain size of 102 mu m and 6.45 mu m. Both materials have similar room temperature dielectric constants (similar to 2000), but PZFNT shows higher remnant polarization (similar to 15 mu C/cm(2)) and better pyroelectric properties (similar to 1.69 . 10(-4) C/m(2)K), which recommend it for pyroelectric detectors, infrared radiation- and laser pulse energy-meters.

Lead zirconate titanate doped with iron and niobium (PZFNT) was prepared by conventional processing technique, solid state synthesis method. The influence of dopants on the microstructure, ferroelectric and pyroelectric properties was investigated. XRD data reveals a perovskite structure near to the lead zirconate phase. The relative density of PZFNT is approximate 90%, with average grains size of 6.45 mu m.

Ferroelectric field effect transistors (FeFETs) based on lead zirconate titanate (PZT) ferroelectric material and amorphous-indium-gallium-zinc oxide (a-IGZO) were developed and characterized. The PZT material was processed by a sol-gel method and then used as ferroelectric gate. The a-IGZO thin films, having the role of channel semiconductor, were deposited by radio-frequency magnetron sputtering, at a temperature of similar to 50 degrees C. Characteristics of a typical field effect transistor with SiO2 gate insulator, grown on highly doped silicon, and of the PZT-based FeFET were compared. It was proven that the FeFETs had promising performances in terms of I-on/I-off ratio (i.e., 10(6)) and IDS retention behavior.

We investigate how far the hysteresis-free behavior of perovskite solar cells can be reproduced using particular pre-conditioning and measurement conditions. As there are currently more and more reports of perovskite solar cells without J-V hysteresis it is crucial to distinguish between genuine performance improvements and measurement artifacts. We focus on two of the parameters that influence the dynamic J-V scans, namely the bias scan rate and the bias poling voltage, and point out measurement conditions for achieving a hysteresis-free behavior. In this context we discuss the suitability of defining a hysteresis index (HI) for the characterization of dynamic J-V scans. Using HI, aging effects are also investigated, establishing a potential connection between the sample degradation and the variation of the maximal hysteresis on one hand, and the relaxation time scale of the slow process on the other hand. Pre-poling induced recombination effects are identified. In addition, our analysis based on sample pre-biasing reveals potential indications regarding two types of slow processes, with two different relaxation time scales, which provides further insight regarding ionic migration.

Hysteretic effects are investigated in perovskite solar cells in the standard FTO/TiO2/CH3NH3PbI3-xClx/spiro-OMeTAD/Au configuration. We report normal (NH) and inverted hysteresis (IH) in the J-V characteristics occurring for the same device structure, and the behavior strictly depends on the prepoling bias. NH typically appears at prepoling biases larger than the open circuit bias, while pronounced IH occurs for negative bias prepoling. The transition from NH to IH is marked by an intermediate mixed hysteresis behavior characterized by a crossing point in the J-V characteristics. The measured J-V characteristics are explained quantitatively by the dynamic electrical model. Furthermore, the influence of the bias scan rate on the NH/IH hysteresis is discussed based on the time evolution of the accumulated ionic and electronic polarization charge at the interfaces. Introducing a three-step measurement protocol, which includes stabilization, prepoling, and measurement, we put forward the difficulties and possible solutions for a correct photoconversion efficiency evaluation.

The integration of ferroelectrics in perovskite solar cells is proposed as possible way to enhance charge collection efficiency. First results on solar cellmanufactured with PbTiO3 (PTO) instead of TiO2 have shown negligible values for the power conversion efficiency (PCE). This is explained by the high serial resistance of sol-gel deposited PTO on F:SnO2 electrodes (FTO). Although PTO layer has remnant polarization of 22 mu C/cm(2), the high potential barrier (0.25 +/- 0.05 eV) at the FTO/PTO interface and lowcarriermobility (10(-8) cm(2) V-1 s(-1)) compared to TiO2 leads to high serial resistance. Better results were obtained with thinner PTO layers grown by pulsed laser deposition, with PCE values up to 0.6%. Further enhancement was obtained by replacing PTO with BaTiO3 (BTO), with PCE value reaching about 0.8% after poling the cell with +3 V. The most important finding was that the magnitude of the short circuit current increases with the amplitude of the poling voltage while the value of the open-circuit voltage remains about the same, around 0.9 V. This is explained through more efficient collection of the charges generated under illumination in the absorber layer due to the polarization that is present in the ferroelectric film. (C) 2017 Elsevier Ltd. All rights reserved.

Capacitance-voltage (C-V) hysteresis of metal-ferroelectric-semiconductor (MFS) structure based on a-In2GaZnO5.5 and Pb0.2Zr0.8TiO3 layers are recorded in the 350-470 K range. The structure is grown on FTO/glass to obtain a transparent MFS. The memory functionality of the heterostructure is proved through C-V and P-V characteristics. The memory window is dependent on the temperature, the largest value of 2.5 V being obtained at 470 K, where the contribution of the ferroelectric-semiconductor interface defect states is minimized. The direction of C-V hysteresis is clockwise at 350 K, and it turns counterclockwise at higher temperatures where the ferroelectric polarization has the main contribution.

We monitored the evolution in time of pinhole-free structures based on FTO/TiO2/CH3NH3PbI2.6Cl0.4 layers, with and without spiro-OMeTAD and counter electrodes (Ag, Mo/Ag, and Au), aged at 24 degrees C in a dark nitrogen atmosphere. In the absence of electrodes, no degradation occurs. While devices with Au show only a 10% drop in power conversion efficiency, remaining stable after a further overheating at 70 degrees C, >90% is lost when using Ag, with the process being slower for Mo/Ag. We demonstrate that iodine is dislocated by the electric field between the electrodes, and this is an intrinsic cause for electromigration of I- from the perovskite until it reaches the anode. The iodine exhaustion in the perovskite layer is produced when using Ag electrodes, and AgI is formed. We hypothesize that in the presence of Au the iodine migration is limited due to the buildup of I- negative space charge accumulated at the perovskite-OMeTAD interface.

The current-voltage (C-V) characteristic of epitaxial ferroelectric films is simulated assuming the presence of Schottky-type contacts at the two electrode interfaces. The model assumes that the overall capacitance of the metal-ferroelectric-metal (MFM) structure is composed of two parts: (i) one associated with the Schottky contacts, in which the ferroelectric polarization is saturated, the dielectric constant is independent on the voltage and only the linear response to the applied electric field is taken into account; (ii) one related to the ferroelectric volume, where the dielectric constant is voltage dependent through the hysteresis response of the ferroelectric polarization. Themost important result of the model is that it can simulate the experimentally observed thickness dependence of the dielectric constant without considering a so-called "dead layer" at the electrode interface. The model renders C-V characteristics in good qualitative agreement with the experimental ones in the case of an MFM structure based on epitaxial PZT films. The quantitative fit suggests that the behaviour of the ferroelectric polarization during the C-V measurement may be very different from its behaviour during the hysteresis measurement. This is explained by the fact that the two measurements have very different principles. It is also found that the dielectric constant of the ferroelectric volume has a different voltage dependence compared to the one derived from the hysteresis loop or from the experimental C-V characteristic. This is also related to the different measurement principles and to the fact that the measured capacitance of the MFM structure includes, besides the ferroelectric volume, the voltage dependent capacitance of the Schottky contacts. (C) 2015 Elsevier B.V. All rights reserved.

An amplification of near three orders of magnitude was observed in Pb(Zr,Ti)O-3 (PZT) thin films deposited on Pt/Si substrates when the Si substrate is included as an impedance in series with the PZT capacitor. The effect is present only at wavelengths below 1100 nm, where the incident light can be absorbed in the Si substrate with generation of free carriers. These carriers in turns modulate the internal electric field inside the ferroelectric layer leading to a much larger variation of the polarization compared to the one generated only by the temperature variation. This fact leads to a considerable enhancement of the pyroelectric signal. The finding can be useful in designing pyroelectric detectors with enhanced characteristics for visible and near infrared region of the electromagnetic spectrum.

Europium doped zinc oxide (Eu:ZnO) thin films have been obtained by pulsed laser deposition (PLD). 002 textured thin films were achieved on glass and silicon substrates, while hetero-epilayers and homo-epilayers have been attained on single crystal SrTiO3 and ZnO, respectively. X-ray Diffraction (XRD) was employed to characterize the Eu:ZnO thin films. Extended XRD studies confirmed the different thin film structural properties as function of chosen substrates.

The results of the electric and magnetic measurements performed on PbZr0.2Ti0.8O3-BiFeO3 symmetric structures, deposited on Pt/Si wafers, were compared for different number of layers in order to analyse the effect of interfaces over the macroscopic properties. It was found that the shape and magnitude of the capacitance-voltage characteristic, as well as the shape and parameters of the ferroelectric and magnetic hysteresis, depend on the number of interfaces in the intended multilayer structure. A temperature induced gradual transition from a magnetically disordered spin glass like phase of low temperature to an uncompensated antiferromagnetic phase at room temperature takes place in the BiFeO3 films, under low applied magnetic fields. A partial ferromagnetic like order can be obtained at low temperatures by increasing the field. The observed changes in the electric and magnetic behaviour of the systems were related to an increased degree of disorder for electric dipoles and magnetic moments, due to the increased number of layers and crystallization treatments. (C) 2011 Elsevier B.V. All rights reserved.

The paper presents the influence of pulsed laser deposition (PLD) parameters on the structural and optical properties of PZT thin films grown on platinum substrate. X-ray diffraction (XRD), spectroscopic ellipsometry (SE) and X-ray photoelectron spectroscopy (XPS) are used to determine the thin film properties. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) are employed to get additional information. By changing the distance between target and substrate, different crystalline orientations of PZT are obtained. The thin film thickness and its roughness, as well as the refractive index are also influenced by the chosen distance. (C) 2011 Elsevier B.V. All rights reserved.

Pt-ZnO-Pb(Zr0.2Ti0.8)O-3-Pt (PZT-ZnO) heterostructures were fabricated by using a sol-gel process. Capacitance-voltage measurements performed on a wide temperature range (20-450 K) have revealed the presence of a hysteresis that undergo a change of direction from clockwise at temperatures below 350 K to counter-clockwise at higher temperatures. In the first case, the hysteresis is produced by charge injection, similar to the case of classical metal-oxide-semiconductor capacitors. In the last case, the hysteresis is the fingerprint of polarization reversal, as reported for metal-ferroelectric-semiconductor (MFS) structures based on n-Si. The memory window at 450 K is about 6 V. This result suggests that PZT-ZnO MFS heterostructures can be used for memory devices working at elevated temperatures, in which the ZnO plays the role of the semiconductor.

The short-circuit photocurrent was measured in ferroelectric capacitors of polycrystalline and epitaxial quality. The interest was to study the possible relation between photocurrent and back-switching phenomena due to ferroelectric polarization imprint, as suggested by Pintilie [J. Appl. Phys. 101, 064109 (2007)]. An interesting relation between the shape of the ferroelectric hysteresis loop and the shape of the photocurrent spectral distribution was found. In polycrystalline samples, the shape of spectral distribution and the sign of photocurrent are changing in time, although the hysteresis is almost symmetrical. However, the hysteresis is not rectangular as in the case of epitaxial films. This behavior suggests a subtle relation between polarization back-switching and photocurrent. In epitaxial samples a peculiar dependence between photocurrent and polarization imprint was found. All these are explained assuming the presence of an internal field, possibly generated by charged defects, which can change its direction and magnitude under illumination, with consequence on the orientation and magnitude of the ferroelectric polarization, and on the sign/shape of the short-circuit photocurrent spectral distribution. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3445877]

A single ferroelectric Schottky diode was obtained on a SrRuO3-Pb(Zr0.2Ti0.8)O-3-Ta (SRO-PZT20/80-Ta) structure in which the SRO-PZT20/80 interface is the rectifying contact and the PZT20/80-Ta interface behaves as a quasiohmic contact. Both the capacitance-voltage (C-V) and the current-voltage (I-V) characteristics show the memory effect due to the ferroelectric polarization. However, retention studies had revealed that only the "down" orientation of ferroelectric polarization is stable in time (polarization oriented from top to bottom contact). The analysis of the experimental results suggests that the PZT20/80 is n type and that the stable orientation of polarization is related to the presence of a depletion region at the SRO-PZT20/80 Schottky interface.

PbZr0.2Ti0.8O3-BiFeO3-PbZr0.2Ti0.8O3 (PZT-BFO-PZT) structure was prepared by sol-gel method on Pt/Si wafers. Three metals were tested as top electrod: Au, Cu, and Pt. A double hysteresis loop was observed in all cases, suggesting an antiferroelectric-like behavior. The values for remnant polarization and coercive field are about 3 mu C/cm(2) and 115 kV/cm, respectively. The saturation polarization is about 22 mu C/cm(2). Capacitance and leakage current show significant dependence on the top metal electrode. The results were explained considering the presence of a Schottky-type contact at the PZT-metal interface.

Pb(Zr0.2Ti0.8)O-3-BiFeO3 (PZT-BFO) multilayer structures were realized by sol-gel on Pt/Si substrate and their electrical properties were investigated using top Pt, Au and Cu electrodes. All multilayers start and end with PZT films. The polarization-voltage and current-voltage hysteresis loops resemble to those encountered in case of antiferroelectric (AFE) films, although component materials are both ferroelectric (FE). The AFE-like behavior is more clearly visible in the case of three-layer structures of PZT-BFO-PZT type, and it is not dependent of the metal used as top electrode. After fatigue cycling the polarization hysteresis apparently changes from characteristic AFE double-loop to FE single loop, although the four switching current peaks characteristic for an AFE behavior are still present in the current hysteresis. These results suggest the presence of an AFE interfacial coupling between the PZT and BFO layers.

Leakage currents determine bumps in the capacitance-voltage characteristics of metal-oxide-semiconductor-type heterostructures with capacitance values larger than the insulator capacitance. A nearly parallel shift with frequency is also observed. These aspects are connected with the presence of a high density of interface states. We illustrate these effects for the case of nano-PbS/SiO2/Si heterostructures. The phenomena were simulated and we propose a method to quickly estimate the interface state density level of a heterostructure when leakage channels are present. (C) 2008 American Institute of Physics.

Pb(Zr1-xTix)O-3 (PZT) thin films were prepared by sol-gel method on stainless steel (SS) and on platinum-coated silicon substrate (Pt/Si). The structure revealed by X-ray diffraction shows strong crystallographic orientation: (110) and (100), respectively. The crystallite size shows significant differences: d((00l))((SS))= 27.1 nm, d((h00))((Pt)) = 88 nm. The tetragonal splitting is (Delta c/c)((ss))=3.55 % and (Delta c/c)((pt))=3.32 %. The ferroelectric hysteresis loop in the static mode is characterized by remanentpolarization of 25 mu C/cm(2) and coercive field of 45 kV/cm for SS substrate, while for Pt/Si substrate the values are 10 mu C/cm(2) and 39 kV/cm, respectively. The leakage current is about 3 orders of magnitude lower in the PZT film deposited on SS. The better properties of the PZT deposited on SS are explained by the presence of large single crystal-like crystallites, which make the film closer to epitaxial ones. The results show the potential of growing epitaxial films on low-price substrates such as stainless-steel.

Self assembled InGaAs/GaAs quantum dots (QD) have a great potential for high performance optoelectronic devices such as low threshold laser diodes, infrared detectors, modulators, memories. In order to characterize the behavior of the QD system, we use two p(+)-n structures grown epitaxially on GaAs under similar conditions. The first structure acts as reference while in the second structure a single QD self-assembled layer is introduced in the middle of the n-GaAs matrix layer. The structure is designed such that for OV applied bias the QD layer lies outside the depleted region. When the reverse bias is increased, the charge from the QD system is removed and the depletion layer moves further into the GaAs matrix material. The electronic structure of the QD is investigated using two methods: photoluminescence, in order to characterize the transition energies between electron and hole levels in the QD system and capacitance spectroscopy in order to study the electron levels in the conduction band only. In addition, admittance spectroscopy spectra are measured in order to characterize the carrier transport mechanism. There is no evident step in the capacitance versus frequency behavior at room temperature in the range 1 Hz-1 MHz, indicating a large carrier cross section caption and/or a low activation energy for the carrier transport between the dot system and the wetting layer and GaAs barriers. The plateau in the C-V behavior, due to charging or discharging of the QD system is modeled using the solution of a Poisson equation and the resulting energy of the electron states within the conduction band and QD size distribution are correlated with results from photoluminescence studies, which involve transitions between energy levels both from the conduction and valence bands.

The nano-crystalline PbS/n-Si heterostructure was studied using photocurrent spectra, I-V and C-V characteristics and admittance spectroscopy. The frequency dependent junction capacitance and conductance measurements show the presence of two contributions: first, a defect related mechanism which we attribute to a deep trap level with a large cross-section in nano-crystals with smaller sizes around 5 nm at the interface with Si and a second mechanism with an activation energy of about 250 meV, attributed to carrier transport in relatively large PbS grains of about 15 nm in size. (c) 2007 Elsevier B.V. All fights reserved.

The influence of the gate voltage on photoconductivity in P-Si/SiO2/(nano)crystalline PbS, Metal-Oxide Semiconductor Field-Effect Transistor (MOSFET)-like structures is investigated. The effect on the photo-signal in the wavelength range 500-1180 nm is opposite compared to the effect in the wavelength range 1600-2500 nm: a negative gate voltage increases the signal in the short wavelength range and decreases it for the long wavelength range. The opposite is valid for a positive gate bias. An on-off ratio better than 85 times is obtained for the spectral range 500-1180 nm, corresponding to the absorption in p-Si and better than 3.5 times for the spectral range 1600-2500 nm corresponding to the absorption in the (nano)crystal line PbS region, respectively. (c) 2007 Elsevier B.V. All rights reserved.

The PbS micro-crystalline and nano-crystalline films were obtained using the Chemical Bath Deposition method. We investigated comparatively the structural, electrical and photoconductive properties of these films deposited on glass. PbS/SiO2/Si heterostructures made with nanocrystalline PbS layers present interesting peculiarities. Their C-V curves show hysterezis. In a field effect arrangement it is possible to control the photoconductive short and long wavelength ratio response. The heterostructure properties were explained by taking into account the interface charged traps.

The mechanism of charge storage in p Si/SiO2 /nano-crystalline PbS heterostructures is investigated using capacitance - voltage (C-V) and conductance-voltage (G-V) measurements at different frequencies. The nano-crystalline thin PbS films were obtained using the Chemical Bath Deposition method with a shorter reaction time and without doping element in the reducing bath. The C-V curves show hysterezis indicating charge storage with a maximum charge density of 3x10(11) cm(-2) for the highest measurement frequency of 100 kHz. The charge storage capacity is enhanced in the rase of using a nano-crystalline PbS thin film instead of a standard macro-crystalline film.

The PbS/SiO2/Si structures show a clockwise hysteresis of capacitance-voltage (C-V) characteristics. The loop width increases with temperature and sweep time. The conductance-voltage (G-V) characteristics also present a hysteresis effect with two bumps. Both characteristics show a strong shift with frequency. We show that these effects are determined by the positive mobile ions injected in the oxide region during the chemical bath deposition of PbS and by the high concentration Of Si/SiO2 interface states. The corresponding C-V and G-V characteristics are simulated and the main peculiarities of the experimental results are well reproduced by the modeled curves.

Pb(Zr1-xTix)O-3 (PZT) thin films were prepared by sol-gel method on stainless steel (SS) and on platinum-coated silicon substrate (Pt/Si). The structure revealed by X-ray diffraction shows strong crystallographic orientation: (110) and (100), respectively. A small amount of pyrochlore phases (Pb-2(Zr,Ti)(2)O6-delta is formed in the films deposited on SS substrate. The crystallite size shows significant differences: d((00l))((SS)) = 27.1 nm, d((h00))((Pt)) = 88 nm. The tetragonal splitting is (Delta c/c)((SS)) = 3.55 % and (Delta c/c)((Pt)) = 3.32 %.

The sol-gel deposition method has been successfully applied to obtain Pb(Zr0.2Ti0.8)03 thin films on platinized silicon wafers. Addition of different amounts (7-15 wt.%) of organic macromolecular polyvinylpyrrolidone in the precursor solution prior to spin coating proves to be an excellent method for obtaining porous films. The crystal structure of as deposited films was analyzed by X-ray diffraction. The porous films show perovskite phase after annealing at 650 degrees C. The surface morphology has been studied by Atomic Force Microscopy and Scanning Electron Microscopy. The surface profile indicates a roughness of the film of 5 nm and no microcracks on the surface. The ferroelectric behavior was proved for each film, by hysteresis loops and by the "butterfly" shape of the capacitance-voltage characteristics. The remnant polarization and the coercive field decrease while the amount of added PVP increases. (C) 2006 Elsevier B.V. All rights reserved.

A new method for the preparation of PbS/PZT composite materials is proposed. The PZT matrix has been obtained using the sol-gel method on Pt-coated Si substrates. The PbS (nano) crystals were subsequently obtained by dipping the porous PZT matrix in Pb(NO3)(2) and Na2S solutions at room temperature. The XRD spectra show the presence of the tetragonal phase of PZT. The microstructure of the film was analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The size of the PbS (nano)-particles at the sample's surface is about 25 nm, estimated from the AFM analysis. The roughness of the sample's surface is about 5 nm. The porosity of the composite, estimated from the SEM analysis in cross-section is smaller than for the reference PZT porous matrix. The equivalent dielectric constant of the composite increases by a factor of 4-5 in comparison with the porous PZT reference and does not depend on the thickness of the surface PbS (nano)-crystalline layer. The saturated polarization (Ps) value for the PZT-PbS composite is smaller than that corresponding to the bulk PZT but higher than for the reference porous PZT. We attribute these effects to the partial filling of the pores in the PZT matrix with PbS.

A comparative study of photodetector performance for nano- and micro-crystalline PbS thin layers is presented Both types of PbS films were obtained using the Chemical Bath Deposition method. To prepare nano-crystalline thin films we used a short reaction time with no doping Bi added At low levels of irradiance (0.1 mW/cm(2)) and room temperature (RT), the macro-crystalline PbS outperforms its nano-crystalline counterpart, by a factor of 6 for the value of Delta R/R-dark. However the nano-crystalline photodetectors show significantly lower optical quenching for large values of irradiance (approximate to 500 mW/cm(2)) at RT and better Delta R/R-dark performance at lower temperature, with an optimum temperature Of 150 K. The low frequency noise behavior is a superposition of 1/f flicker noise at low frequency and generation-recombination and thermal noise at higher frequency. The proportionaliiy factor between the 1/f noise and the DC dark current for the series resistor is 1.5 times larger for the nano-crystalline photodetector at room temperature.

Nanocrystalline PbS thin films were grown on glass substrates using Chemical Bath Deposition (CBD) method. The presence of nanocrystals was revealed by optical absorption and photocurrent measurements. We have compared the absorption threshold between large size and nanocrystalline PbS. Our study was performed in order to demonstrate that the size of the PbS thin films crystallites affects the photoelectric properties of the material. Using the Scanning Electron Microscopy (SEM) we have determined that the grains inside large size PbS crystallites are 300 nm. From the optical absorption measurements we have determined that the size of PbS nanocrystals is between 5-50 nm. The photoconduction measurements show that large size PbS has a maximum in infrared situated at 2.4 mu m, and in PbS nanocrystalline thin film this maximum is shifted toward smaller wavelengths towards visible and near infrared.

PbZr1-XTiXO3 (PZT) film was prepared by addition of polymer polyvinylpirrolidone (PVP) in the PZT precursor and hydrolysis of the PZT precursor sol. Porous thin films were prepared by spin coating on Pt-coated Si substrate. The structure of the films was investigated by X-ray diffraction (XRD). (100)-oriented PZT 20180 film was obtained by hydrolysis of sol. PVP addition leads to the (110)-orientation of the film. The surface microstructure of the films was characterised with Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). The surface profile indicates a films roughness of 5 nm. No micro-cracks were observed on film surface. The average remnant polarization and the coercive field were obtained from the hysteresis loop measurements. The ferroelectric behavior has been evidenced by the presence of the butterfly shape of the capacitance-voltage characteristics. Experimental results show that the dielectric constant of the PZT porous film is lower than that of the dense film.