National Institute Of Materials Physics - Romania

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.

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.

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.

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.

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.

Cu2SnSe3 (CTSe) is a polyvalent material that can be used as an absorber layer for thin film solar cells or as a starting layer for the synthesis of CZTSe or CZTSSe compounds. Obtaining CTSe single phase films with opti-mized properties for thin film solar cells is a difficult task. A systematic study using both metallic and binary chalcogenides precursors for the formation of the CTSe phase was not performed. The films consisting of four different stacks (Sn\Cu, SnSe2\Cu, Sn\Cu2Se, and SnSe2\Cu2Se) were prepared by magnetron sputtering on soda lime glass (SLG) and molybdenum (Mo) coated SLG substrates, followed by annealing at 550 degrees C under Sn + Se atmosphere. X-ray diffraction and Raman spectroscopy results indicated the formation of a single CTSe phase in most of the stacks deposited on both substrates. Scanning electron microscopy images showed compact surfaces with large grains in the films deposited on Mo substrate, while the films on SLG have more voids on their sur-faces. The elemental analysis measured by energy dispersive spectroscopy revealed stoichiometric films on Mo, and copper and tin rich compositions on SLG substrates. The band gap values inferred by conventional spec-troscopy are between 0.81 and 1.95 eV. It was found that the SnSe2\Cu and Sn\Cu2Se stacks are preferred for the formation of a single CTSe phase, with dense surface morphology, a stoichiometric composition, and an optimal absorber layer band gap. This study opens the way to comprehend the formation reactions during the seleni-zation of metallic and binary chalcogenides precursors towards the optimization of kesterite absorber for photovoltaic device fabrication.

The paper presents a study concerning the role of ferroelectric filler size and clustering in the dielectric properties of 20%BaTiO3-80%PVDF and of 20% (2%Ag-98%BaTiO3)-PVDF hybrid nanocomposites. By finite element calculations, it was shown that using fillers with epsilon > 103 does not provide a permittivity rise in the composites and the effective dielectric constant tends to saturate to specific values determined by the filler size and agglomeration degree. Irrespective of the ferroelectric filler sizes, the addition of metallic ultrafine nanoparticles (Ag) results in permittivity intensification and the effect is even stronger if the metallic nanoparticles are connected to a higher degree with the ferroelectric particles' surfaces. When using coarse ferroelectric fillers, the probability of clustering is higher, thus favoring the permittivity increase by field concentration in small regions close to the interfaces separating dissimilar materials. The modeling results were validated by an experimental dielectric analysis performed in a series of PVDF-based thick films with the same amount of BaTiO3 fillers or with Ag-BaTiO3 hybrid fillers. Similar trends as predicted by simulations were found experimentally but with slightly higher permittivity values which were assigned to the modifications of the polymer phase composition due to the presence of nanofillers and the local sample inhomogeneity (the presence of clustering, in particular for coarse BaTiO3 grains), which create regions with enhanced local fields.

The paper presents a study concerning the role of ferroelectric filler size and clustering in the dielectric properties of 20%BaTiO3-80%PVDF and of 20% (2%Ag-98%BaTiO3)-PVDF hybrid nanocomposites. By finite element calculations, it was shown that using fillers with epsilon > 103 does not provide a permittivity rise in the composites and the effective dielectric constant tends to saturate to specific values determined by the filler size and agglomeration degree. Irrespective of the ferroelectric filler sizes, the addition of metallic ultrafine nanoparticles (Ag) results in permittivity intensification and the effect is even stronger if the metallic nanoparticles are connected to a higher degree with the ferroelectric particles' surfaces. When using coarse ferroelectric fillers, the probability of clustering is higher, thus favoring the permittivity increase by field concentration in small regions close to the interfaces separating dissimilar materials. The modeling results were validated by an experimental dielectric analysis performed in a series of PVDF-based thick films with the same amount of BaTiO3 fillers or with Ag-BaTiO3 hybrid fillers. Similar trends as predicted by simulations were found experimentally but with slightly higher permittivity values which were assigned to the modifications of the polymer phase composition due to the presence of nanofillers and the local sample inhomogeneity (the presence of clustering, in particular for coarse BaTiO3 grains), which create regions with enhanced local fields.