National Institute Of Materials Physics - Romania

The development of kesterite (Cu2ZnSn(S,Se)4, CZTSSe) thin films for photovoltaic applications is highly necessary, given their composition of Earth-abundant, environmentally friendly elements and their compatibility with established photovoltaic technologies. This study presents a novel synthesis approach for CZTSSe films with varied S/(S+Se) ratios, ranging from 0.83 to 0.44, by a two-step magnetron sputtering deposition/annealing process. The first step consists in an initial deposition of stacked Mo/SnS2/Cu layers, which, upon thermal treatment in a sulfur atmosphere, were transformed into Cu2SnS3 (CTS) films. In the second step, further deposition of ZnSe and subsequent annealing in a tin and selenium atmosphere resulted in the formation of a CZTSSe phase. These processes were optimized to fabricate high-quality and single-phase CZTSSe films, thereby mitigating the formation of secondary phases. Characterization techniques, including scanning electron microscopy, demonstrated a clear correlation between decreased S/(S+Se) ratios and enhanced film densification and grain size. Moreover, grazing incidence X-ray diffraction and Raman spectroscopy confirmed a compositional and structural transition from close to CZTS to nearly a CZTSe phase as the S/(S+Se) ratios decreased. This study advances kesterite-based solar cell technology by enhancing the structural properties and crystallinity of the absorber layer, necessary for improving photovoltaic performance.

The compounds KBa 1-x Sr x Cr 2 (PO 4 ) 3 (with x = 0.00; 0.25; 0.50; 0.75; 1.00) were synthesized by a solid-state reaction, and they were thoroughly characterized by different spectroscopic and microscopic techniques. Their structures were indexed in a cubic system with a P2 1 3 space group forming a 3D framework built on CrO 6 octahedra and PO 4 tetrahedra sharing vertices leading to identical Cr 2 P 3 O 18 (U) units. The interconnection between the tetrahedral and octahedral groups leads to the formation of two large closed cavities (K, M II )(1) and (K, M II )(2), statistically occupied by K + and M 2+ (M = Ba, Sr) atoms. Electron paramagnetic resonance spectroscopy confirmed the presence of paramagnetic Cr 3+ ions, showing the effects of substituting the Ba 2+ ions with smaller Sr 2+ ions on the dipolar coupling between the Cr 3+ centers. The obtained materials and active carbon were used as electrode materials in hybrid SC devices. At the same time, their electrochemical properties were assessed by potentiostatic electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge measurements, showing promising results with a maximal specific capacitance (3.86 F/g), energy density (343 mWh/kg), and power density (30.9 kW/kg) in the case of KBa 0.5 Sr 0.5 Cr 2 (PO 4 ) 3 , proving them as good candidates for positive and/or negative electrode materials for energy storage applications.

Quaternary multicomponent Cu2BaSnS4 (CBTS) has emerged as a potential absorber material due to its abundant and nontoxic constituents, high absorption coefficient (10-4 cm-1) and suitable bandgap (1.5-2.0 eV) for the solar photovoltaic application. In this study, polycrystalline CBTS thin layers have been deposited by a typical spray pyrolysis technique on glass substrates using different substrate temperatures (Ts = 200, 250, 300 and 350 degrees C) followed by annealing in a sulfur-rich atmosphere at 550 degrees C under an argon flow. The (micro-)structural, compositional, and optical properties of both types of films have been studied. Analysis of x-ray diffractogram (XRD) patterns for all acquired films showed the presence of polycrystalline CBTS alongside various secondary phases, including Cu2SnS3 being predominant. Nonetheless, the XRD of the films deposited at 250 degrees C and annealed at 550 degrees C showed only the CBTS phase. Raman spectroscopy confirm the formation of the trigonal phase of CBTS. The presence of Cu, Ba, Sn and S in CBTS thin films was confirmed by X-ray photoelectron spectroscopy and Energy-dispersive X-ray spectroscopy. Scanning electron micrographs show a smooth and dense structure with enhanced crystallinity and improved uniformity. Overall, the physical properties of CBTS thin films were found to be spray deposition temperature dependent. An appropriate optical band gap of 1.6 to 1.8 eV and a compact structure indicate their prospective for solar cell applications.

Carbon monoxide (CO) is reversibly adsorbed on and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate. All processes are characterized in real time via photoelectron spectroscopy. Adsorption proceeds on different sites/geometries as a function of substrate temperature. Below room temperature, CO is adsorbed on surface Ba. At room temperature, adsorption proceeds on surface oxygen, whereas at high temperatures, "hollow" site adsorption occurs with carbon coordinated with three oxygens, one oxygen initially belonging to CO and two oxygens from the substrate. The amount of CO adsorbed is about one molecule for 10 surface unit cells, which is slightly increased at low temperatures. CO is desorbed if the substrate is heated above the Curie temperature, which is a sign of the definitory role of ferroelectric polarization. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption.

This paper describes the electrical and dielectric behavior of the nCdS/pZnTe HJ by current-voltage, capacitance-voltage characteristics, and impedance spectroscopy in a temperature interval 220-350 K. A microcrystalline p-ZnTe layer and n-CdS were grown on glass/ZnO substrate by closed space sublimation method. As frontal contact to CdS, the transparent ZnO and as a back contact to ZnTe, silver conductive paste (Ag) treated at 50 degrees C in vacuum were used. The current-voltage results of nCdS/pZnTe HJ show a rectifying behavior. The junction ideality factor, barrier height, and series resistance values were extracted from the rectifying curves at different temperatures. The built-in voltage, carrier concentration and depletion width were obtained from the capacitance-voltage measurements. Analysis of the J-V-T and C-V-T characteristics shows that the thermionic emission and recombination current flow mechanisms dominate in the nCdS/pZnTe HJ. The dielectric study reveals that the experimental values of the AC conductivity, dielectric constant, dielectric loss, the imaginary part of the electric modulus are found to be very sensitive to frequency and temperature. The dielectric constant and dielectric loss are observed to be high at the low frequency region. The increase in the values of electric modulus with the frequency implies an increase in the interfacial polarization at the interface of nCdS/pZnTe HJ. Jonscher's universal power law shows that with increasing frequency, AC conductivity increased. The results conductivity show that the ionic conductivity and interfacial polarization are the main parameters affecting the dielectric properties of the device when the temperature changes.

Recently, a smart strategy for two-dimensional (2D) materials synthesis has emerged, namely space-confined chemical vapor deposition (CVD). Its extreme case is the microreactor method, in which the growth substrate is face-to-face stacked on the source substrate. In order to grow 2D transition metal dichalcogenides by this method, transition metal oxides, dispersed in very small amounts on the source substrate, are used as source materials in most of the published reports. In this paper, a colloidal dispersion of MoS2 in saline solution is used and MoS2 nanosheets with various shapes, sizes (between 5 and 60 mu m) and thicknesses (2-4 layers) have been synthesized. Small MoS2 flakes (regular or defective) are present on the surface of the nanosheets. Catalytic sites, undercoordinated atoms located at the edges of MoS2 flakes and nanosheets, are produced in a high number by a layer-plus-island (Stranski-Krastanov) growth mechanism. Several double-resonance Raman bands (at 147, 177, 187, 225, 247, 375 cm(-1)) are assignable to single phonon processes in which the excited electron is elastically scattered on a defect. The narrow 247 cm(-1) peak is identified as a topological defect-activated peak. These findings highlight the potential of defect engineering in material property optimization, particularly for solar water splitting applications.

Carbon monoxide (CO) is reversibly adsorbed on and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate. All processes are characterized in real time via photoelectron spectroscopy. Adsorption proceeds on different sites/geometries as a function of substrate temperature. Below room temperature, CO is adsorbed on surface Ba. At room temperature, adsorption proceeds on surface oxygen, whereas at high temperatures, "hollow" site adsorption occurs with carbon coordinated with three oxygens, one oxygen initially belonging to CO and two oxygens from the substrate. The amount of CO adsorbed is about one molecule for 10 surface unit cells, which is slightly increased at low temperatures. CO is desorbed if the substrate is heated above the Curie temperature, which is a sign of the definitory role of ferroelectric polarization. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption.

The present study aims to describe the role of the grain size on the properties of submicron- and nano-structured Ba0.8Sr0.2TiO3 (BST) ceramics. Dense (1 - 2% porosity) ceramics with average grain sizes in the range of (77 234) nm were consolidated under different spark plasma sintering conditions starting from nanopowders with a mean particle size of 70 nm, synthesized via the acetate variant of the sol-gel method. The structural analysis based on XRD data revealed a mixture of cubic and tetragonal modifications at room temperature for the precursor powders and for all the investigated ceramics. The structural heterogeneity of the individual ceramic grains with coexistence of cubic and tetragonal polymorphs was confirmed by HR-TEM investigations. Accordingly, a "brick-wall" model with cubic grain boundary regions and tetragonal grain cores is proposed. By increasing the grain size, from 77 to 234 nm, a decrease of the phase transitions diffuseness accompanied by an increase of the permittivity maxima (from 650 to 4500) and dielectric losses (from 5 to 7.5%, at 100 Hz), was detected by broadband dielectric spectroscopy. No variation of the Curie temperature in the investigated Ba0.8Sr0.2TiO3 ceramics was detected, unlike typically reported for BaTiO3 ceramics with similar grain sizes. The Curie-Weiss temperature and the Curie constant decrease when grain size is diminished, indicating an overall reduction of the ferroelectric active volume, as a scaling effect. The ferroelectric switching was demonstrated for all the selected fine-grained BST ceramics, either at nanoscale or macroscopically, with an increased ferroelectric character for the coarser submicron-structured ceramics, with respect to the nanocrystalline one. The observed properties of the fine-grained Ba0.8Sr0.2TiO3 ceramics are explained in the frame of multiphase coexistence and ferroelectricity "dilution" due to the increasing role of non-ferroelectric grain boundaries when reducing grain size and complete the knowledge on the scale-dependent properties of dense fine-grained BaTiO3-based ceramics.

Considering the increasing need for sustainable and economical energy storage solutions, the integration of layered materials such as MoS2 into these systems represents an important step toward enhancing energy sustainability and efficiency. Exploring environmentally responsible fabrication techniques, this study assesses wrinkled MoS2 thin films synthesized from distinct Mo and MoS2 targets, followed by sulfurization conducted in a graphite box. We utilized magnetron sputtering to deposit precursor Mo and MoS2 films on Si substrates, achieving thicknesses below 20 nm. This novel approach decreases sulfur by up to tenfold during sulfurization due to the confined space technique, contributing also to avoiding the formation of toxic gases such as SO2 or the necessity of using H2S, aligning with sustainable materials development. Thinner MoS2 layers were obtained post-sulfurization from the MoS2 precursors, as shown by X-ray reflectometry. Raman spectroscopy and grazing X-ray diffraction analyses confirmed the amorphous nature of the as-deposited films. Post-sulfurization, both types of films exhibited crystalline hexagonal MoS2 phases, with the sulfurized Mo showing a polycrystalline nature with a (100) orientation and sulfurized MoS2 displaying a (00L) preferred orientation. The X-ray photoelectron spectroscopy results supported a Mo:S ratio of 1:2 on the surface of the films obtained using the MoS2 precursor films, confirming the stoichiometry obtained by means of energy dispersive X-ray spectroscopy. Scanning electron microscopy and atomic force microscopy images revealed micrometer-sized clusters potentially formed during rapid cooling post-sulfurization, with an increased average roughness. These results open the way for the further exploration of wrinkled MoS2 thin films in advanced energy storage technologies.