National Institute Of Materials Physics - Romania

This paper reports the synthesis and characterization of Cu2ZnSnS4 (CZTS) absorber films, prepared by a two-step electrodeposition of a ZnS (zinc sulfide) binary and a CZT (copper, zinc and tin) ternary precursors on Mo/Ti/Si substrates. The as-electrodeposited ZnS/CZT and CZT/ZnS stacks were thermally treated in a tubular furnace in sulfur environment at 550 degrees C. The role of the ZnS buffer layer is to provide a zinc and sulfur reservoir, needed to complete the formation of kesterite phase. X-ray diffraction and Raman analyses revealed the formation of the CZTS phase. The surface morphology and chemical composition of the films were studied using a scanning electron microscope. The bandgap values inferred from diffuse reflectance data, are discussed with respect to the stoichiometry which is considerably affected by the order of the stacks. Room-temperature photoluminescence of the CZT/ZnS sample showed a board PL band of 1.51 eV. It was found that the film with a ZnS layer on top is preferred for the formation of a Zn-rich single CZTS phase.

Complex ferroelectric structures with dielectric interlayers may become possible alternatives for neuromorphic computing and low-power field-effect transistors since they exhibit multiple polarization states and negative capacitance. However, the effects on the switching characteristics due to the electric properties of the nonferroelectric circuit element have not been clearly evaluated so far. A high-resistance or low-capacitance element is usually associated with an increased depolarization field and eventually with suppression of polarization but without further consideration of the electrostatic differences. Therefore, we show that switching behavior is dramatically changed if the non-FE element is a resistive component or a capacitive one. This is reflected by either an increased apparent coercive field or imprint, respectively. A negative capacitance regime was observed at different moments but strongly depends on the nature of the nonferroelectric element. The voltage on the ferroelectric component remains constant during switching, which is a fingerprint of the system passing through non-equilibrium states. Therefore, we propose an algorithm to recover the S-shape of polarization dependence on the ferroelectric internal voltage during the slowed transition between the two stable states of polarization.

In this work, the thermally stimulated current (TSC) technique has been used to investigate the properties of the radiation-induced interstitial boron and interstitial oxygen defect complex by 23-GeV (E-kin) protons, including activation energy, defect concentration, as well as the annealing behavior. At first isothermal annealing (at 80 degrees C for 0-180 min) followed by isochronal annealing (for 15 min between 100 degrees C and 190 degrees C in steps of 10 degrees C), studies had been performed in order to get information about the thermal stability of the interstitial boron and interstitial oxygen defect in 50-Omega cm material after irradiation with 23-GeV protons to a fluence of 6.91 x 10(13) p/cm(2). The results are presented and discussed. Furthermore, the extracted data from TSC measurements are compared with the macroscopic properties derived from current-voltage and capacitance-voltage characteristics. In addition, the introduction rate of interstitial boron and interstitial oxygen defect as a function of the initial doping concentration was determined by exposing diodes with different resistivities (10, 50, 250, and 2 k Omega cm) to 23-GeV protons. These results are compared with data from TSC and deep-level transient spectroscopy measurements achieved by the team of the CERN-RD50 "Acceptor removal project."

In the last decade orthorhombic hafnia and zirconia films have attracted tremendous attention arising from the discovery of ferroelectricity at the nanoscale. However, an initial wake-up pre-cycling is usually needed to achieve a ferroelectric behaviour in these films. Recently, different strategies, such as microstructure tailoring, defect, bulk and interface engineering, doping, NH3 plasma treatment and epitaxial growth, have been employed to obtain wake-up free orthorhombic ferroelectric hafnia and zirconia films. In this work we review recent developments in obtaining polar hafnia and zirconia-based thin films without the need of any wake-up cycling. In particular, we discuss the rhombohedral phase of hafnia/ zirconia, which under a constrained environment exhibits wake-up-free ferroelectric behaviour. This phase could have a strong impact on the current investigations of ferroelectric binary oxide materials and pave the way toward exploiting ferroelectric behaviour for next-generation memory and logic gate applications. Crown Copyright (c) 2022 Published by Elsevier Ltd. All rights reserved.

The role of Ag addition on the structural, dielectric, and mechanical harvesting response of 20%(xAg - (1 - x)BaTiO3) - 80%PVDF (x = 0, 2, 5, 7 and 27 vol.%) flexible composites is investigated. The inorganic fillers were realized by precipitating fine (similar to 3 nm) silver nanoparticles onto BaTiO3 nanoparticles (similar to 60 nm average size). The hybrid admixtures with a total filling factor of 20 vol.% were embedded into the PVDF matrix. The presence of filler enhances the amount of beta-PVDF polar phase and the BaTiO3 filler induces an increase of the permittivity from 11 to 18 (1 kHz) in the flexible composites. The addition of increasing amounts of Ag is further beneficial for permittivity increase; with the maximum amount (x = 27 vol.%), permittivity is three times larger than in pure PVDF (epsilon(r) similar to 33 at 1 kHz) with a similar level of tangent losses. This result is due to the local field enhancement in the regions close to the filler-PVDF interfaces which are additionally intensified by the presence of silver nanoparticles. The metallic addition is also beneficial for the mechanical harvesting ability of such composites: the amplitude of the maximum piezoelectric-triboelectric combined output collected in open circuit conditions increases from 0.2 V/cm(2) (PVDF) to 30 V/cm(2) for x = 27 vol.% Ag in a capacitive configuration. The role of ferroelectric and metallic nanoparticles on the increasing mechanical-electric conversion response is also been explained.

Anodization was used to obtain a nanotubular TiO2 photoanode on F-SnO2 glass. Subsequent annealing in the CH4 atmosphere promoted the C-doping and improved the crystallinity of the TiO2 nanotubes. The pulsed laser deposition was applied to cover the nanotubes with Bi2O3, serving as a hole transport material. X-ray photoelectron spectroscopy analyses of the doped samples reveal a shift in the valence band's maximum position towards lower binding energy as compared to those observed for the undoped samples (annealed in the air). The doping positively affects the absorption by shifting the absorption edge to 567 nm. I-V measurements under illumination show that the C-doping of TiO2 increases the current density following the absorbance results. The highest open circuit voltage was reached for the samples with the 300 degrees C-deposited Bi2O3 layer, pointing to better quality of the p-n junction, hence of the contact between Bi2O3 and TiO2. This in situ annealing provided the formation of close contact between Bi2O3 and TiO2, which enabled a faster charge transport as compared to the contact obtained with no annealing or even with post annealing.

Zr0.8Sn0.2TiO3 (ZST) powders synthesized by solid-state reaction were subject to processing by spark plasma sintering (SPS). A single-phase ceramic with a high relative density of 95.7% and 99.6% was obtained for sintering temperatures of 1150 degrees C and 1200 degrees C, respectively, and for a dwell time of 3 min. In order to reduce the oxygen vacancies, as-sintered discs were annealed in air at 1000 degrees C. The dielectric loss of the annealed samples, expressed by the Q x f product, measured in the microwave (MW) domain, varied between 35 THz and 50 THz. The intrinsic losses (Q x f ~ 60 THz) were derived by using terahertz time-domain spectroscopy (THz-TDS).

Ag/Ga were incorporated into resorbable orthopaedic phosphate bioactive glasses (PBG, containing P, Ca, Mg, Na, and Fe) thin films to demonstrate their potential to limit growth of Staphylococcus aureus and Escherichia coli in post-operative prosthetic implantation. Dual target consecutive co-sputtering was uniquely employed to produce a 46 nm Ag:PBG composite observed by high resolution TEM to consist of uniformly dispersed similar to 5 nm metallic Ag nano-particles in a glass matrix. Ga3+ was integrated into a phosphate glass preform target which was magnetron sputtered to film thicknesses of similar to 400 or 1400 nm. All coatings exhibited high surface energy of 75.4-77.3 mN/m, attributed to the presence of hydrolytic P-O-P structural surface bonds. Degradation profiles obtained in deionized water, nutrient broth and cell culture medium showed varying ion release profiles, whereby Ga release was measured in 1400 nm coating by ICP-MS to be similar to 6, 27, and 4 ppm respectively, fully dissolving by 24 h. Solubility of Ag nanoparticles was only observed in nutrient broth (similar to 9 ppm by 24 h). Quantification of colony forming units after 24 h showed encouraging antibacterial efficacy towards both S. aureus (4-log reduction for Ag:PBG and 6-log reduction for Ga-PBG approximate to 1400 nm) and E. coli (5-log reduction for all physical vapour deposited layers) strains. Human Hs27 fibroblast and mesenchymal stem cell line in vitro tests indicated good cytocompatibility for all sputtered layers, with a marginal cell proliferation inertia in the case of the Ag:PBG composite thin film. The study therefore highlights the (i) significant manufacturing development via the controlled inclusion of metallic nanoparticles into a PBG glass matrix by dual consecutive target co-sputtering and (ii) potential of PBG resorbable thin-film structures to incorporate and release cytocompatible/antibacterial oxides. Both architectures showed prospective bio-functional performance for a future generation of endo-osseous implant-type coatings.

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.

This work reports the effect of the rapid solidification technique and thermal treatment on the martensitic transformation (MT), magnetic and magnetostrictive properties on the off-stoichiometric Ni49Mn31Ga20 and Ni51Mn28Ga21 ferromagnetic shape memory ribbons. The samples were investigated by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, magnetic and magnetostrictive measurements. The temperature dependence of the X-ray phases analysis shows the presence of martensite structures, both tetragonal and monoclinic, at room temperature and allowed to study their evolution through MT. The thermal treatment induces changes in the microstructure with implications in MT and Curie temperatures evolution. The competition between the magnetization orientation and twin boundary motion within martensitic variants under magnetic field evidenced in the magnetic-strain curves was discussed and correlated with the magnetic data.