In the quest for advanced materials suitable for next-generation electronic and optoelectronic applications, tungsten disulfide (WS2) ultrathin films have emerged as promising candidates due to their unique properties. However, obtaining WS2 directly on the desired substrate, eliminating the need for transfer, which produces additional defects, poses many challenges. This paper aims to explore the synthesis of WS2 ultrathin films via physical vapor deposition (PVD) followed by sulfurization in a confined space, addressing the challenge of film formation for practical applications. Precursor layers of tungsten and WS2 were deposited by RF magnetron sputtering. Subsequent sulfurization treatments were conducted in a small, closed, graphite box to produce WS2 films. The physical and chemical properties of these precursor and sulfurized layers were thoroughly characterized using techniques such as X-ray reflectometry (XRR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The findings reveal notable distinctions in film thickness, structural orientation, and chemical composition, attributable to the different precursor used. Particularly, the sulfurized layers from the tungsten precursor exhibited a preferred orientation of WS2 crystallites with their (00L) planes parallel to the substrate surface, along with a deviation from parallelism in a small angular range. This study highlights the necessity of precise control over deposition and sulfurization parameters to tailor the properties of WS2 films for specific technological applications.

One of the new materials for next-generation thin film solar cells is Cu2ZnSnSe4 (CZTSe). However, achieving a single-phase CZTSe compound remains a challenge. This study describes the development of Cu2ZnSnSe4 thin films through the sequential deposition of stacked films of non-stoichiometric Cu2SnSe3 (CTSe) and ZnSe by magnetron sputtering. The structural, morphological, and electrical properties as well as the surface chemistry of the films were investigated and compared depending on the growth sequence of the thin films. By using Raman spectroscopy and grazing incidence X-ray diffraction, the tetragonal CZTSe structure was confirmed. Scanning electron microscopy and energy-dispersive spectroscopy measurements of the morphological and compositional properties indicated large grains and dense surfaces with an elemental composition close to the desired stoichiometry in SLG\SnSe2\Cu\ZnSe and SLG\SnSe2\Cu2Se\ZnSe stacks. To ascertain the surface chemistry and unique characteristics of the produced films, additional X-ray photoemission spectroscopy experiments were carried out. The optimal band gap values for the absorber layers were found using conventional spectroscopy, and they ranged from 0.88 to 1.47 eV. According to the electrical measurements, all the films were p-type and have high carrier concentrations between 1016 and 1020 cm-3. Our findings demonstrate that employing a sequential deposition approach and annealing in different atmospheres can yield CZTSe absorber layers with desirable properties, overcoming the challenge of non-stoichiometric CTSe precursors.

Cu2ZnSnSe4 thin films have been synthesized by employing two magnetron-sputtering depositions, interlaced with two sequential post-deposition heat treatments in low vacuum, Sn+Se and Se-rich atmospheres at 550 degrees C. By employing successive structural analysis methods, namely Grazing Incidence X-Ray Diffraction (GIXRD) and Raman Spectroscopy, secondary phases such as ZnSe coexisting with the main kesterite phase have been identified. SEM peered into the surface morphology of the samples, detecting structural defects and grain profiles, while EDS experiments showed off-stoichiometric elemental composition. The optical bandgaps in our samples were calculated by a widely used extrapolation method from recorded transmission spectra, holding values from 1.42 to 2.01 eV. Understanding the processes behind the appearance of secondary phases and occurring structural defects accompanied by finding ways to mitigate their impact on the solar cells' properties is the prime goal of the research beforehand.

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 current study aims to present and discuss the results obtained by complementary archaeometric methods applied for the first time on white pigments inlaid on excised pottery of the Boian-Vidra tradition (Early Chalcolithic, c. 4900-4600 BCE). The samples came from three settlements located in Southern Romania (Sultana-Ghetarie, Vidra, and Vladiceasca). They were selected considering that the pottery was produced in approximately contemporary sites, located relatively close to each other in the same geographical region, namely the Romanian Plain. The experimental part included the analysis of local samples of carbonate concretions and prehistoric animal bone ash as reference materials. Archaeometric investigations consisted in applying "in-air" PIXE and EDX methods for the chemical composition, XRD and FTIR for mineralogical data, SEM for microstructure observation, and EPR for the characterisation of the paramagnetic centres. Calcite, bone ash, and silica rich sediments were identified as the primary decorating pigments. The mixtures of calcite and bone-ash observed in 13 samples were specific to the sites at Vidra and Vladiceasca. Silica-rich sediments from distant sources were the main whitening materials in two samples from Vladiceasca, while for the samples from Sultana-Ghetarie, calcite was the only whitening mineral. The results show with a high degree of confidence the use of both local (i.e., carbonate neo-formations and bone ash) and exotic (silica-rich sediments) raw materials to obtain the white pigment applied to Boian-Vidra pottery. Thus, the current data show the adaptability of the potters with respect to the surrounding resources and also provide new evidence for a vast trade network of raw materials and/or finished products in the Lower Danube area during the Early Chalcolithic. The deliberate mixing of two whitening materials from different sources could be a technological choice and may highlight complex symbolic behaviours.

Cu2ZnSnS4 (CZTS) is regarded as one of the emerging materials for next-generation thin film solar cells. However, its synthesis is complex, and obtaining a single-phase CZTS thin film is difficult. This work reports the elaboration of Cu2ZnSnS4 thin films by a sequential magnetron sputtering deposition of Cu2SnS3 (CTS) and ZnS as stacked films. Initially, the CTS films were prepared on a soda lime glass substrate by annealing Cu and SnS2 stacked layers. Second, ZnS was deposited by magnetron sputtering on the CTS films. The CTS\ZnS stacks were then annealed in Sn + S or S atmospheres. The tetragonal CZTS structure was obtained and confirmed by grazing incidence X-ray diffraction and Raman spectroscopy. The morphological and compositional characteristics, measured by scanning electron microscopy and energy-dispersive spectroscopy, revealed large grains and dense surfaces with the elemental composition close to the intended stoichiometry. Additional X-ray photoemission spectroscopy measurements were performed to determine the surface chemistry and particularities of the obtained films. The optical properties, determined using conventional spectroscopy, showed optimal absorber layer band gap values ranging between 1.38 and 1.50 eV. The electrical measurements showed that all the films are p-type with high carrier concentrations in the range of 10(15) to 10(20) cm(-3). This new synthesis route for CZTS opens the way to obtain high-quality films by an industry-compatible method.

Cu2SnS3 (CTS) is emerging as a promising absorber for the next generation thin film solar cells (TFSC) due to its excellent optical and electronic properties, earth-abundance and eco-friendly elemental composition. In addition, CTS can be used as precursor films for the Cu2ZnSnS4 (CZTS) synthesis. The optical properties of CTS are influenced by stoichiometry, crystalline structure, secondary phases and crystallite size. Routes for obtaining CTS films with optimized properties for TFSC are still being sought. Here, the CTS thin films synthesized by magnetron sputtering on soda lime glass (SLG) using Cu and SnS2 targets in two different stacks, were studied. The SLG\Cu\SnS2 and SLG\SnS2\Cu stacks were annealed in S and Sn + S atmospheres, at various temperatures. Both stacks show a polymorphic structure, and higher annealing temperatures favor the monoclinic CTS phase formation. Morphology is influenced by the stacking order since a SnS2 top layer generates several voids on the surface due to the evaporation of SnS, while a Cu top layer provides uniform and void-free surfaces. The films in the copper-capped stack annealed under Sn + S atmosphere have the best structural, morphological, compositional and optical properties, with tunable band gaps between 1.18 and 1.37 eV. Remarkably, secondary phases are present only in a very low percent (< 3.5%) in samples annealed at higher temperatures. This new synthesis strategy opens the way for obtaining CTS thin films for solar cell applications, that can be used also as intermediary stage for CZTS synthesis.

Understanding the phonon anharmonicity and temperature-dependent behavior of phonons that affect the thermal transport properties in 2D materials is crucial for developing efficient thermoelectric and memristor devices. SnSe has attracted significant interest because of its potential applications for developing such novel devices. Here, orthorhombic SnSe nanoflakes with a thickness of less than 100 nm and oriented along the [100] crystal axis were obtained using physical vapor transport at atmospheric pressure. Polarization-resolved Raman spectroscopy of SnSe nanoflakes was performed at a temperature of 5 K. Temperature-dependent frequencies and linewidths of Raman modes in tin selenide were fitted according to the anharmonic phonon coupling theory. The results indicate that both two and three order processes are responsible for the phonon decay in tin selenide. The memristive property was confirmed by electrical measurements of SnSe devices. SnSe memristors have an operating current of 10-4 A, similar to other transition-metal dichalcogenide memristors, but are more energy efficient than memristors based on defect migration, with a threshold voltage of 3 V.

The consumer market requests infrared (IR) optical components, made of relatively abundant and environmentally friendly materials, to be integrated or attached to smartphones. For this purpose, three new chalcogenides samples, namely Ge23.3Zn30.0Se46.7 (d_GZSe-1), Ge26.7Zn20.0Se53.3 (d_GZSe-2) and Ba4.0Ge12.0Zn17.0Se59.0I8.0 (d_GZSe-3) were obtained by mechanical alloying and processed by spark plasma sintering into dense bulk disks. Obtaining a completely amorphous and homogeneous material proved to be difficult. d_GZSe-2 and d_GZSe-3 are glass-ceramics with the amount of the amorphous phase being 19.7 and 51.4 wt. %, while d_GZSe-1 is fully polycrystalline. Doping with barium and iodine preserves the amorphous phase formed by milling and lowers the sintering temperature from 350 degrees C to 200 degrees C. The main crystalline phase in all of the prepared samples is cubic ZnSe or cubic Zn0.5Ge0.25Se, while in d_GZSe-3 the amorphous phase contains GeSe4 clusters. The color of the first two sintered samples is black (the band gap values are 0.42 and 0.79 eV), while d_GZSe-3 is red (E-g is 1.37 eV) and is transparent in IR domain. These results are promising for future research in IR materials and thin films.

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.

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.

Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.

Ge2Sb2Te5 (GST-225) is a chalcogenide material with applications in nonvolatile memories. However, chalcogenide material properties are dependent on the deposition technique. GST-225 thin films were prepared using three deposition methods: magnetron sputtering (MS), pulsed laser deposition (PLD) and a deposition technique that combines MS and PLD, namely MSPLD. In the MSPLD technique, the same bulk target is used for sputtering but also for PLD at the same time. The structural and optical properties of the as-deposited and annealed thin films were characterized by Rutherford backscattering spectrometry, X-ray reflectometry, X-ray diffraction, Raman spectroscopy and spectroscopic ellipsometry. MS has the advantage of easily leading to fully amorphous films and to a single crystalline phase after annealing. MS also produces the highest optical contrast between the as-deposited and annealed films. PLD leads to the best stoichiometric transfer, whereas the annealed MSPLD films have the highest mass density. All the as-deposited films obtained with the three methods have a similar optical bandgap of approximately 0.7 eV, which decreases after annealing, mostly in the case of the MS sample. This study reveals that the properties of GST-225 are significantly influenced by the deposition technique, and the proper method should be selected when targeting a specific application. In particular, for electrical and optical phase change memories, MS is the best suited deposition method.

Sn nanoparticles (NPs) are usually obtained by difficult chemical routes in several steps followed by thermal treatments. Here, a simple and clean method, to obtain Sn NPs directly on the substrate, is developed based on a vapor transport technique. The method is versatile, thus can be easily adjusted to obtain Sn NPs of different size, areal density and morphology, by controlling the deposition conditions. NPs are grown on Si/SiO2 substrate and characterized. Water contact angle measurements show that Sn nanoparticles increase the surface hydrophobicity by 20%. Thus, NPs cleanly obtained from a low-cost, earth-abundant, and environmentally friendly material, can be used to modulate the wettability of surfaces. (C) 2020 Elsevier B.V. All rights reserved.