Andrei TOMULESCU

Herein we present a comparative study among different spray-coated nanometric mesoporous electron transporting layers (ETLs) in perovskite solar cells (PSC), namely m-TiO2, 2 , m-SnO2 2 and m-SnO2 2 quantum dots (mSnO2QDs). 2 QDs). The solutions used for deposition were prepared from commercial pastes and colloidal suspensions for m-TiO2 2 and m-SnO2. 2 . For m-SnO2QDs 2 QDs in-house QDs solutions were prepared. The formamidiniummethylamonium-potassium (FAMA@10 K) has been used as light absorber material in the fabricated PSCs. The structural, compositional and morphological studies, correlated with the photovoltaic performance of PSCs, indicate that the m-SnO2 2 QDs layer is the best candidate among the three investigated mesoporous ETLs. Compared with the suspensions used for the other two ETLs, the in-house prepared SnO2 2 QDs solution presents smaller agglomerates of nanoparticles and results in the formation of a thinner, more uniform and compact mesoporous ETL. The FAMA@10 K perovskite deposited on m-SnO2 2 QDs ETL presents a lower roughness, better uniformity and a higher amount of PbI2. 2 . Our work unveils that the SnO2 2 QDs solution can be easily produced in laboratory and when is deposited as mesoporous scaffold in a PSC with FAMA@10 K perovskite, the power conversion efficiency increases up to 14.90 %, being with up to 27 % larger than in the PSCs with m-TiO2 2 and mSnO2 2 ETLs prepared from commercial solutions. By modeling the J-V dynamic hysteresis with more than 90 % match between the calculated and experimental J-V data, for all three types of mesoporous ETLs, the relevant parameters that explain the hysteresis magnitude and account for ionic-induced recombination processes in PSCs were determined.

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.

Interest in self-cleaning coatings is rising due to their potential to enhance comfort and quality of life in polluted urban environments, driving the search for materials with optimal physical properties. Convergent with this goal, this study investigates the wetting properties and photo-catalytic efficiency of reticulated TiO2 layers. It shows that these properties are significantly influenced by the topographical characteristics of the TiO2 surface, which can be precisely controlled through variations in pulverization pressure and low-temperature post-annealing treatments. Post-deposition annealing of the TiO2 layers achieves 100 % self-cleaning efficiency for both thick and thin films, with optical transmission ranging from approximately 60 %-80 % in the visible spectrum. Additionally, the TiO2 layers exhibited promising capabilities for eliminating pathogenic microorganisms and disinfecting surfaces. The underlying causal factors of these remarkable and technologically promising surface features are explored and discussed.

This paper evidences research results on a new technology for deposition of TiO2 nanostructured layers on glass. Air pollution, industrialization and everyday life activities are factors that point towards the need for efficient and ergonomic cleaning process of the impressive glazing surfaces that surround people in modern offices, leisure places and not the least, in houses. The design of equipment, the innovative technique based on pneumatically spraying a suspension of TiO2 nanocrystals, the process parameters and preliminary test results for the obtained layers stand as main topics for the article. Integration of the system into industry 4.0 virtual intelligent platform is also presented. Further research development in order to validate the nanostructured TiO2 coating on glazed surfaces is aimed.

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.

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%.

Dynamic hysteresis effects have been long known to occur in the current density-voltage characteristics of perovskite solar cells, with the ionic migration being identified as the primary factor. The hysteretic effects impacted early studies by the uncertainty in the evaluation of the power conversion efficiency, while currently, potential links to degradation mechanisms are the focus. Therefore, understanding ion migration is a central goal, typically addressed by performing a combined large and small signal analysis. The reported large capacitive and inductive effects created controversies with respect to the underlying mechanisms, yielding essentially two classes of models, one based on the large accumulation capacitances and the other based on the ionic modulation of the collected current. We introduce here an equivalent circuit model and interpret these phenomena in terms of recombination current modulation, identifying the distinct contributions from ion current and ionic charge accumulations. These contributions to the recombination current are associated with capacitive and inductive effects, respectively, and we corroborate the numerical simulations with electrochemical impedance spectroscopy measurements. These show the role of the recombination currents of photogenerated carriers in producing both capacitive and inductive effects as the illumination is varied. Moreover, we provide a bridging point between the two classes of models and suggest a framework of investigation of defect states based on the observed inductive behavior, which would further aid the mitigation of the degradation effects.

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.

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.

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%.

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.

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.

A carbon-based layer was deposited by spraying on top of a ferroelectric layer grown by sol-gel on Si (001) substrate and its properties as electrode and absorber for pyroelectric detection were tested. It was found that the electric properties of the ferroelectric capacitor with top carbon-based sprayed electrode (CBSE) are comparable with those of the capacitors with standard top SrRuO3 (SRO)/Au electrode. Pyroelectric measurements show that the pyroelectric signal recorded on ferroelectric capacitors with top CBSE electrode is 2.5 times greater than for top SRO/Au electrode for low frequency range. The value of the pyroelectric coefficient was estimated to 9.73.10(-4) C/m(2)K for CBSE electrodes and 3.36.10(-4) C/m(2)K for SRO/Au respectively. The fabrication process of CBSE is of low cost, easy to implement and with high throughput making it attractive for manufacturing various devices like pyroelectric detector, thermal imaging, solar cells, etc.

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.

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.

The dynamic effects observed in the J-V measurements represent one important hallmark in the behavior of the perovskite solar cells. Proper measurement protocols (MPs) should be employed for the experimental data reproducibility, in particular for a reliable evaluation of the power conversion efficiency (PCE), as well as for a meaningful characterization of the type and magnitude of the hysteresis. We discuss here several MPs by comparing the experimental J-V characteristics with simulated ones using the dynamic electrical model (DEM). Pre-poling conditions and bias scan rate can have a dramatic influence not only on the apparent solar cell performance, but also on the hysteretic phenomena. Under certain measurement conditions, a hysteresis-free behavior with relatively high PCEs may be observed, although the J-V characteristics may be far away from the stationary case. Furthermore, forward-reverse and reverse-forward bias scans show qualitatively different behaviors regarding the type of the hysteresis, normal and inverted, depending on the bias pre-poling. We emphasize here that correlated double-scans, forward-reverse or reverse-forward, where the second scan is conducted in the opposite sweep direction and begins immediately after the first scan is complete, are essential for a correct assessment of the dynamic hysteresis. In this context, we define a hysteresis index which consistently assigns the hysteresis type and magnitude. Our DEM simulations, supported by experimental data, provide further guidance for an efficient and accurate determination of the stationary J-V characteristics, showing that the type and magnitude of the dynamic hysteresis may be affected by unintentional pre-conditioning in typical experiments.

A dynamic electrical model is introduced to investigate the hysteretic effects in the J-V characteristics of perovskite based solar cells. By making a simple ansatz for the polarization relaxation, our model is able to reproduce qualitatively and quantitatively detailed features of measured J-V characteristics. Pre-poling effects are discussed, pointing out the differences between initially over- and under-polarized samples. In particular, the presence of the current overshoot observed in the reverse characteristics is correlated with the solar cell pre-conditioning. Furthermore, the dynamic hysteresis is analyzed with respect to changing the bias scan rate, the obtained results being consistent with experimentally reported data: the hysteresis amplitude is maximum at intermediate scan rates, while at very slow and very fast ones it becomes negligible. The effects induced by different relaxation time scales are assessed. The proposed dynamic electrical model offers a comprehensive view of the solar cell operation, being a practical tool for future calibration of tentative microscopic descriptions. (C) 2016 Elsevier B.V. All rights reserved.

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.

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.