National Institute Of Materials Physics - Romania

Polycrystalline NiO thick film-based gas sensors have been exposed to different test gas atmospheres at 250 degrees C and measured via simultaneous electrical resistance and work function investigations. Accordingly, we decoupled different features manifested toward the potential changes, i.e., work function, band-bending, and electron affinity. The experimental results have shown that the presence of moisture induces an unusual behavior toward carbon monoxide (CO) detection by considering different surface adsorption sites. On this basis, we derived an appropriate detection mechanism capable of explaining the lack of moisture influence over the CO detection with NiO-sensitive materials. As such, CO might have both chemical and dipolar interactions with pre-adsorbed or lattice oxygen species, thus canceling out the effect of moisture. Additionally, morphology, structure, and surface chemistry were addressed, and the results have been linked to the sensing properties envisaging the role played by the porous quasispherical-hollow structures and surface hydration.

Preventing and controlling the spread of multidrug-resistant (MDR) bacteria implicated in healthcare-associated infections is the greatest challenge of the health systems. In recent decades, research has shown the need for passive antibacterial protection of surfaces in order to reduce the microbial load and microbial biofilm development, frequently associated with transmission of infections. The aim of the present study is to analyze the efficiency of photocatalytic antimicrobial protection methods of surfaces using the new photocatalytic paint activated by light in the visible spectrum. The new composition is characterized by a wide range of analytical methods, such as UV-VIS spectroscopy, electron microscopy (SEM), X-ray powder diffraction (PXRD) or X-ray photoelectron spectroscopy (XPS). The photocatalytic activity in the UV-A was compared with the one in the visible light spectrum using an internal method developed on the basis of DIN 52980: 2008-10 standard and ISO 10678-2010 standard. Migration of metal ions in the composition was tested based on SR EN1186-3: 2003 standard. The new photocatalytic antimicrobial method uses a type of photocatalytic paint that is active in the visible spectral range and generates reactive oxygen species with inhibitory effect against all tested microbial strains.

In this work, a multi-analytical approach involving nitrogen porosimetry, small angle neutron and X-ray scattering, Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies, X-ray diffraction, thermal analysis and electron microscopy was applied to organically modified silica-based xerogels obtained through the sol-gel process. Starting from a tetraethoxysilane (TEOS) precursor, methyltriethoxysilane (MTES) was added to the reaction mixture at two different pH values (2.0 and 4.5) producing hybrid xerogels with different TEOS/MTES molar ratios. Significant differences in the structure were revealed in terms of the chemical composition of the silica network, hydrophilic/hydrophobic profile, particle dimension, pore shape/size and surface characteristics. The combined use of structural characterization methods allowed us to reveal a relation between the cavity dimensions, the synthesis pH value and the grade of methyl substitution. The effect of the structural properties on the controlled Captopril release efficiency has also been tested. This knowledge facilitates tailoring the pore network for specific usage in biological/medical applications. Knowledge on structural aspects, as reported in this work, represents a key starting point for the production of high-performance silica-based hybrid materials showing enhanced efficacy compared to bare silica prepared using only TEOS.

The advancement of nanotechnology in the last decade has developed an abundance of novel and intriguing TiO2-based nanomaterials that are widely used in many sectors, including industry (as a food additive and colorant in cosmetics, paints, plastics, and toothpaste) and biomedicine (photoelectrochemical biosensing, implant coatings, drug delivery, and new emerging antimicrobial agents). Therefore, the increased use of engineered nanomaterials in the industry has raised serious concern about human exposure and their unexpected cytotoxic effects. Since inhalation is considered the most relevant way of absorbing nanomaterials, different cell death mechanisms induced in MRC-5 lung fibroblasts, following the exposure to functionalized TiO2 NPs, were investigated. Long-term exposure to TiO2 nanoparticles co-doped with 1% of iron and nitrogen led to the alteration of p53 protein activity and the gene expression controlled by this suppressor (NF-kB and mdm2), DNA damage, cell cycle disruptions at the G2/M and S phases, and lysosomal membrane permeabilization and the subsequent release of cathepsin B, triggering the intrinsic pathway of apoptosis in a Bax- and p53-independent manner. Our results are of major significance, contributing to the understanding of the mechanisms underlying the interaction of these nanoparticles with in vitro biological systems, and also providing useful information for the development of new photocatalytic nanoparticles that are active in the visible spectrum, but with increased biocompatibility.

Cu2ZnSnS4 (CZTS) is a complex quaternary material, and obtaining a single-phase CZTS with no secondary phases is known to be challenging and dependent on the production technique. This work involves the synthesis and characterization of CZTS absorber layers for solar cells. Thin films were deposited on Si and glass substrates by a combined magnetron sputtering (MS) and pulsed laser deposition (PLD) hybrid system, followed by annealing without and with sulfur powder at 500 degrees C under argon (Ar) flow. Three different Cu2S, SnS2, and ZnS targets were used each time, employing a different target for PLD and the two others for MS. The effect of the different target arrangements and the role of annealing and/or sulfurization treatment were investigated. The characterization of the absorber films was performed by grazing incidence X-ray diffraction (GIXRD), X-ray reflectometry (XRR), Raman spectroscopy, scanning electron microscopy, and regular transmission spectroscopy. The film with ZnS deposited by PLD and SnS2 and Cu2S by MS was found to be the best for obtaining a single CZTS phase, with uniform surface morphology, a nearly stoichiometric composition, and an optimal band gap of 1.40 eV. These results show that a new method that combines the advantages of both MS and PLD techniques was successfully used to obtain single-phase Cu2ZnSnS4 films for solar cell applications.

The feasibility of mixed-cation mixed-halogen perovskites of formula A(x)A'1-xPbXyXz'X3-y-z '' is analyzed from the perspective of structural stability, opto-electronic properties and possible degradation mechanisms. Using density functional theory (DFT) calculations aided by machine-learning (ML) methods, the structurally stable compositions are further evaluated for the highest absorption and optimal stability. Here, the role of the halogen mixtures is demonstrated in tuning the contrasting trends of optical absorption and stability. Similarly, binary organic cation mixtures are found to significantly influence the degradation, while they have a lesser, but still visible effect on the opto-electronic properties. The combined framework of high-throughput calculations and ML techniques such as the linear regression methods, random forests and artificial neural networks offers the necessary grounds for an efficient exploration of multi-dimensional compositional spaces.

Surface plasmon resonance containing amorphous As2S3 film is proposed as a chemical sensor to highlight several liquid hydrocarbons. Method is label-free and is based on detection of small changes in the refractive index. As2S3 operates as plasmonic waveguide which confines the probing beam to the interface with liquid hydrocarbons. The method can easily distinguish hydrocarbons with very close refractive indices. The film thicknesses were optimized to obtain the best sensitivity and resolving power Minimum reflectance of SPR less than 1 % was found for optimal calculated film thicknesses, the sensitivity to the refractive index changes being 2.10(-5).

High-quality ZnS thin films as buffer layer have been successfully synthesized and simulated using the low-cost Mist CVD technique and the SCAPS-1D software for different deposition times (30, 40, 50, and 60 min). The structural, morphological, and optical properties of the prepared ZnS films have been investigated using X-ray diffraction (XRD), scanning electronic microscopy (SEM), atomic force microscopy (AFM), and UV-Vis spectrophotometer. The time deposition effect on ZnS films' efficiency as a buffer layer has been evaluated. XRD pattern confirms the hexagonal/cubic structure of the prepared samples, with (111) as preferred orientation. Raman spectra confirm XRD findings by the two peaks located at 348 cm(-1) and 697 cm(-1) which correspond to ZnS samples' cubic and hexagonal structures. Scanning electronic microscopy (SEM) and atomic force microscopy (AFM) images show densely uniform grains with precise shapes and boundaries covering the entire sample's surface with a relative roughness for all deposition times. The optical transmittance shows an average of 78% in the visual field of light with an optical band gap varying between 3.69 and 3.80 eV. Numerical simulation of ZnO:Al/ZnS/CZTS/Mo cell using SCAPS-1D software shows that the sample deposited for 30 min presents the best performance with an efficiency of up to 8.9%.

ZnS is a wide band gap material which was proposed as a possible candidate to replace CdS as a buffer layer in solar cells. However, the structural and optical properties are influenced by the deposition method. ZnS thin films were prepared using magnetron sputtering (MS), pulsed laser deposition (PLD), and a combined deposition technique that uses the same bulk target for sputtering and PLD at the same time, named MSPLD. The compositional, structural, and optical properties of the as-deposited and annealed films were inferred from Rutherford backscattering spectrometry, X-ray diffraction, X-ray reflectometry, Raman spectroscopy, and spectroscopic ellipsometry. PLD leads to the best stoichiometric transfer from target to substrate, MS makes fully amorphous films, whereas MSPLD facilitates obtaining the densest films. The study reveals that the band gap is only slightly influenced by the deposition method, or by annealing, which is encouraging for photovoltaic applications. However, sulphur vacancies contribute to lowering the bandgap and therefore should be controlled. Moreover, the results add valuable information towards the understanding of ZnS polymorphism. The combined MSPLD method offers several advantages such as an increased deposition rate and the possibility to tune the optical properties of the obtained thin films.

In this work, the structural, thermal, vibrational, morphological, magnetic and optical properties of LaPO4:Ce/RE/Me (RE=Nd3+, Tb3+; Me-Cr3+, Mn2+) and LaPO4:Yb3+/Er3+ phosphors prepared by the co-precipitation method are presented. The obtained materials crystallized in monoclinic structure with the P2(1)/n space group and the particles were of nanorod shape with about 200 nm in length and the diameter approximately 19 nm. The presence of dopant ions was confirmed by both electron paramagnetic resonance (EPR) and UV-visible spectroscopies. In addition, the down-conversion (DC) and up-conversion (UC) of the LaPO4 nanophosphors via the 275 and 980 nm excitations, respectively, were considered, and a wide range of electronic transitions was observed. Based on the photoluminescence (PL) spectra, there is an efficient energy transfer (ET) process from Ce3+ donors to Nd3+ and Tb3+ acceptors, and the computed ET efficiency was 70% and 88%, respectively. The Ce3+/Cr3+ and Ce3+/Mn2+ doped LaPO4 showed weak far-red and green luminescence with much smaller ET efficiency of about 3.7 and 0.4%, respectively. LaPO4:Yb3+/Er3+ showed UC luminescence under the 980 nm laser radiation, and the resulted red and green light was attributed to the Er3+ transitions.