Dr. Liliana BALESCU

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.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O-3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of similar to 50%), which yielded a promising compressive strength of similar to 20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

This work evaluates the effects of manganese (Mn) doping on the morpho-structural features, mechanical performance, and in vitro biological response of beta-tricalcium phosphate (beta-TCP) derived bioceramics for bone tissue engineering applications. Five different Mn doping levels (i.e., 0.01%, 0.05%, 0.1%, 0.5%, and 1 wt.%) were investigated, with the beta-TCP-based bioceramics being sintered at four temperatures (i.e., 1000, 1100, 1200, and 1300 degrees C). A densification improvement was induced when using Mn in excess of 0.05 wt.%; the densification remained stationary in the sintering temperature range of 1200 - 1300 degrees C. The structural analyses evidenced that all samples sintered at 1000 and 1100 degrees C were composed of beta-TCP as major phase and hydroxyapatite (HA) as a minor constituent (similar to 4-6 wt.%). At the higher temperatures (1200 and 1300 degrees C), the formation of alpha-TCP was signalled at the expense of both beta-TCP and HA. The Mn doping was evidenced by lattice parameters changes. The evolution of the phase weights is linked to a complex inter-play between the capacity of the compounds to incorporate Mn and the thermal decomposition kinetics. The Mn doping induced a reduction in the mechanical performance (in terms of compressive strength, Vickers hardness and elastic modulus) of the beta-TCP-based ceramics. The metabolic activity and viability of osteoblastic cells (MC3T3-E1) for the ceramics were studied in both powder and compacted pellet form. Ceramics with Mn doping levels lower than 0.1 wt.% yielded a more favorable microenvironment for the osteoblast cells with respect to the undoped beta-TCP. No cytotoxic effects were recorded up to 21 days. The Mn-doped beta-TCPs showed a significant increase (p < 0.01) in alkaline phosphatase activity with respect to pure beta-TCP.

Bi-phasic calcium phosphates (BCPs) are considered prominent candidate materials for the fabrication of bone graft substitutes. Currently, supplemental cation-doping is suggested as a powerful path to boost biofunctionality, however, there is still a lack of knowledge on the structural role of such substituents in BCPs, which in turn, could influence the intensity and extent of the biological effects. In this work, pure and Mg- and Sr-doped BCP scaffolds were fabricated by robocasting from hydrothermally synthesized powders, and then preliminarily tested in vitro and thoroughly investigated physically and chemically. Collectively, the osteoblast cell culture assays indicated that all types of BCP scaffolds (pure, Sr- or Sr-Mg-doped) delivered in vitro performances similar to the biological control, with emphasis on the Sr-Mg-doped ones. An important result was that double Mg-Sr doping obtained the ceramic with the highest beta-tricalcium phosphate (beta-TCP)/hydroxyapatite mass concentration ratio of similar to 1.8. Remarkably, Mg and Sr were found to be predominantly incorporated in the beta-TCP lattice. These findings could be important for the future development of BCP-based bone graft substitutes since the higher dissolution rate of beta-TCP enables an easier release of the therapeutic ions. This may pave the road toward medical devices with more predictable in vivo performance.

Currently, there is a considerable time-lag in the industrialisation of innovative technological solutions for the functionalization of osseous implants, with ever-demanding healthcare requirements (e.g., controlled release of therapeutic ions, match of biomaterial degradation - bone growth rates, antimicrobial efficiency). As third-generation biomaterials, phosphate bio-glasses (PBGs) have demonstrated an ability to stimulate specific biological responses from tissue to molecular level, by successfully coupling bioactive and resorbable material properties. Here, radio-frequency magnetron sputtered (RF-MS) PBGs were explored as sacrificial resorbable layers for prospective biomedical implant designs. A PBG powder with a 50-P2O5, 35-CaO, 10-Na2O and 5-Fe2O3 composition (mol%) was used as source (target) material. The influence of the argon working pressure (0.2-1 Pa) - one of the most prominent RF-MS variables - on the morphology, structure, uniformity, composition, degradation rate and cytocompatibility of PBG films was investigated. The engineered modification of physical-chemical and biological features of the PBG sputtered films was multi-parametrically surveyed by AFM, EDXS, spectroscopic ellipsometry, GIXRD, FTIR spectroscopy measurements and in vitro assays. Results suggested that the film thickness, composition, density and structure were preserved over a uniformity region having a diameter of similar to 30 mm, irrespective of sputtering pressure. The network connectivity and the surface porosity of the films were found to have antagonistic roles with respect to the in vitro degradation performance. The possibility of fine tuning the composition, structure and thereby biological interaction of the PBG films by conveniently modifying the sputtering pressure was shown (i.e., permitting their complete controlled degradation, without cytotoxic effects). This work is the first to show in vitro cytocompatibility outcomes of sputtered PBG films and their cross-area uniformity, and thus, it could prove to be an important technological step in their future biomedical application and suggest implications for future industrial scale-up.

Ti6Al4V cranial prostheses in the form of patterned meshes were 3D printed by selective laser melting in an argon environment; using a CO2 laser source and micron-sized Ti6Al4V powder as the starting material. The size and shape of prostheses were chosen based on actual computer tomography images of patient skull fractures supplied in the framework of a collaboration with a neurosurgery clinic. After optimizations of scanning speed and laser parameters, the printed material was defect-free (as shown by metallographic analyses) and chemically homogeneous, without elemental segregation or depletion. The prostheses were coated by radio-frequency magnetron sputtering (RF-MS) with a bioactive thin layer of hydroxyapatite using a bioceramic powder derived from biogenic resources (Bio-HA). Initially amorphous, the films were converted to fully-crystalline form by applying a post-deposition thermal-treatment at 500 degrees C/1 h in air. The X-ray diffraction structural investigations indicated the phase purity of the deposited films composed solely of a hexagonal hydroxyapatite-like compound. On the other hand, the Fourier transform infrared spectroscopic investigations revealed that the biological carbonatation of the bone mineral phase was well-replicated in the case of crystallized Bio-HA RF-MS implant coatings. The in vitro acellular assays, performed in both the fully inorganic Kokubo's simulated body fluid and the biomimetic organic-inorganic McCoy's 5A cell culture medium up to 21 days, emphasized both the good resistance to degradation and the biomineralization capacity of the films. Further in vitro tests conducted in SaOs-2 osteoblast-like cells showed a positive proliferation rate on the Bio-HA RF-MS coating along with a good adhesion developed on the biomaterial surface by elongated membrane protrusions.

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.

We have investigated the structural and electronic properties of the alpha-GeSe surface using atomic force microscopy, scanning tunneling microscopy and density functional theory calculations. GeSe belongs to the group-VI transition metal monochalcogenides and occurs in two polymorphs, alpha-GeSe and beta-GeSe. The most redundant polymorph, alpha-GeSe, has a structure that is very similar to black phosphorene. The alpha-GeSe surface has a centered rectangular unit cell with dimensions a = 3.8 angstrom and b = 4.4 angstrom, respectively. In scanning tunneling microscopy images only the Se atoms are resolved owing to the substantial transfer of electrons from the Ge to the Se surface atoms. This experimental finding is fully in line with density functional theory calculations. Scanning tunneling spectroscopy reveals that the alpha-GeSe surface is a p-type semiconductor with a band gap of 1.0 eV. The GeSe surface is stable at ambient conditions, which makes this material very appealing for technological applications.

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.

High-performance bioceramics are required for preventing failure and prolonging the life-time of bone grafting scaffolds and osseous implants. The proper identification and development of materials with extended functionalities addressing socio-economic needs and health problems constitute important and critical steps at the heart of clinical research. Recent findings in the realm of ion-substituted hydroxyapatite (HA) could pave the road towards significant developments in biomedicine, with an emphasis on a new generation of orthopaedic and dentistry applications, since such bioceramics are able to mimic the structural, compositional and mechanical properties of the bone mineral phase. In fact, the fascinating ability of the HA crystalline lattice to allow for the substitution of calcium ions with a plethora of cationic species has been widely explored in the recent period, with consequent modifications of its physical and chemical features, as well as its functional mechanical and in vitro and in vivo biological performance. A comprehensive inventory of the progresses achieved so far is both opportune and of paramount importance, in order to not only gather and summarize information, but to also allow fellow researchers to compare with ease and filter the best solutions for the cation substitution of HA-based materials and enable the development of multi-functional biomedical designs. The review surveys preparation and synthesis methods, pinpoints all the explored cation dopants, and discloses the full application range of substituted HA. Special attention is dedicated to the antimicrobial efficiency spectrum and cytotoxic trade-off concentration values for various cell lines, highlighting new prophylactic routes for the prevention of implant failure. Importantly, the current in vitro biological tests (widely employed to unveil the biological performance of HA-based materials), and their ability to mimic the in vivo biological interactions, are also critically assessed. Future perspectives are discussed, and a series of recommendations are underlined.