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Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of ≈9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.
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We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.
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The phosphate KCoCr(PO4)2 and iron-substituted variants KCoCr1-xFex(PO4)2 (x = 0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route, while a high substitution level of Fe was achieved. Their structures were refined using powder X-ray diffraction and indexed in a monoclinic system with a P21/n space group. A 3D framework with six-sided tunnels parallel to the [101] direction was formed in which the K atoms are located. Mössbauer spectroscopy confirms the exclusive presence of octahedral paramagnetic Fe3+ ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopy confirmed the presence of paramagnetic Cr3+ ions. The activation energy, determined by dielectric measurements, shows that the iron-containing samples present higher ionic activity. Relative to the electrochemical activity of K, these materials could be good candidates for positive and/or negative electrode materials for energy storage applications.
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Magnetic perovskite films have promising properties for use in energy-efficient spintronic devices and magnetic refrigeration. Here, an epitaxial ferromagnetic La0.67Ba0.33Mn0.95Ti0.05O3 (LBMTO-5) thin film was grown on SrTiO3(001) single crystal substrate by pulsed laser deposition. High-resolution X-ray diffraction proved the high crystallinity of the film with tetragonal symmetry. The magnetic, magnetocaloric and magnetoresistance properties at different directions of the applied magnetic field with respect to the ab plane of the film were investigated. An in-plane uni-axial magnetic anisotropy was evidenced. The LBMTO-5 epilayer exhibits a second-order ferromagnetic-paramagnetic phase transition around 234 K together with a metal-semiconductor transition close to this Curie temperature (TC). The magnetic entropy variation under 5 T induction of a magnetic field applied parallel to the film surface reaches a maximum of 17.27 mJ/cm3 K. The relative cooling power is 1400 mJ/cm3 K (53% of the reference value reported for bulk Gd) for the same applied magnetic field. Giant magnetoresistance of about 82% under 5 T is obtained at a temperature close to TC. Defined as the difference between specific resistivity obtained under 5 T with the current flowing along the magnetic easy axis and the magnetic field oriented transversally to the current, parallel and perpendicular to the sample plane, respectively, the in-plane magneto-resistance anisotropy in 5 T is about 9% near the TC.
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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 1015 to 1020 cm-3. This new synthesis route for CZTS opens the way to obtain high-quality films by an industry-compatible method.
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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 °C to 200 °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 (Eg is 1.37 eV) and is transparent in IR domain. These results are promising for future research in IR materials and thin films.
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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.
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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 °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.
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The discovery of multifunctional properties related to electro-activity of organic systems of biomolecules is important for a variety of applications, especially for devices in the realm of biocompatible sensors and/or bioactuators. A further step towards such applications is to prepare thin films with the required properties. Here, the investigation is focused on the characterization of films of guanine and cytosine nucleobases, prepared by thermal evaporation-an industrial accessible deposition technique. The cytosine films have an orthorhombic non-centrosymmetric structure and grow in two interconnected nanostructured fractal patterns, of nearly equal proportion. Piezoresponse force microscopy images acquired at room temperature on the cytosine films display large zones with antiparallel alignment of the vertical components of the polarization vector. Guanine films have a dense nano-grained morphology. Our studies reveal electrical polarization switching effects which can be related to ferroelectricity in the films of guanine molecules. Characteristic ferroelectric polarization-electric-field hysteresis loops showing large electrical polarization are observed at low temperatures up to 200 K. Above this temperature, the guanine films have a preponderant paraelectric phase containing residual or locally induced nano-scopic ferroelectric domains, as observed by piezoresponse force microscopy at room temperature.
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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.
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Cu2ZnSnS4 (CZTS) is an economically and environmentally friendly alternative to other toxic and expensive materials used for photovoltaics, however, the variation in the composition during synthesis is often followed by the occurrence of the secondary binary and ternary crystalline phases. These phases produce changes in the optical absorption edge important in cell efficiency. We explore here the secondary phases that emerge in a combinatorial Cu2S-ZnS-SnS2 thin films library. Thin films with a composition gradient were prepared by simultaneous magnetron sputtering from three binary chalcogenide targets (Cu2S, SnS2 and ZnS). Then, the samples were crystallized by sulfurization annealing at 450 °C under argon flow. Their composition was measured by energy dispersive X-ray spectroscopy (EDX), whereas the structural and optical properties were investigated by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and optical transmission measurements. As already known, we found that annealing in a sulfur environment is beneficial, increasing the crystallinity of the samples. Raman spectroscopy revealed the presence of CZTS in all the samples from the library. Secondary crystalline phases such as SnS2, ZnS and Cu-S are also formed in the samples depending on their proximity to the binary chalcogenide targets. The formation of ZnS or Cu-S strongly correlates with the Zn/Sn and Cu/Zn ratio of the total sample composition. The presence of these phases produces a variation in the bandgap between 1.41 eV and 1.68 eV. This study reveals that as we go further away from CZTS in the composition space, in the quasi-ternary Cu2S-ZnS-SnS2 diagram, secondary crystalline phases arise and increase in number, whereas the bandgap takes values outside the optimum range for photovoltaic applications.
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This work investigates the structural, magnetic and magneto-optical properties of a new zinc phosphate-tellurite glass belonging to the 45ZnO-10Al2O3-40P2O5-5TeO2 system. The glass was prepared by a wet method of processing the starting reagents followed by suitable melting-stirring-quenching-annealing steps. Specific parameters such as density, average molecular mass, molar volume, oxygen packaging density, refractive index, molar refractivity, electronic polarizability, reflection loss, optical transmission, band gap and optical basicity have been reported together with thermal, magnetic and magneto-optical characteristics. Absorption bands appear in the blue and red visible region, while over 600 nm the glass becomes more transparent. FTIR and Raman spectra evidenced phosphate-tellurite vibration modes proving the P2O5 and TeO2 network forming role. Magnetic measurements reveal the diamagnetic character of the Te-doped glass with an additional weak ferromagnetic signal, specific to diluted ferromagnetic oxides. Positive Faraday rotation angle with monotonous decreasing value at increasing wavelength was evidenced from magneto-optical measurements. The final product is a composite material comprising of a non-crystalline vitreous phase and Te-based nanoclusters accompanied by oxygen vacancies. The metallic-like Te colloids are responsible for the dark reddish color of the glass whereas the accompanying oxygen vacancies might be responsible for the weak ferromagnetic signal persisting up to room temperature.
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In this work, the effects of graphene oxide (GO) concentrations (1.5 wt.%, 2.5 wt.%, and 5 wt.%) on the structural, morphological, optical, and luminescence properties of zinc oxide nanorods (ZnO NRs)/GO nanocomposites, synthesized by a facile hydrothermal process, were investigated. X-ray diffraction (XRD) patterns of NRs revealed the hexagonal wurtzite structure for all composites with an average coherence length of about 40-60 nm. A scanning electron microscopy (SEM) study confirmed the presence of transparent and wrinkled, dense GO nanosheets among flower-like ZnO nanorods, depending on the GO amounts used in preparation. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) absorption spectroscopy, and photoluminescence (PL) measurements revealed the impact of GO concentration on the optical and luminescence properties of ZnO NRs/GO nanocomposites. The energy band gap of the ZnO nanorods was independent of GO concentration. Photoluminescence spectra of nanocomposites showed a significant decrease in the intensities in the visible light range and red shifted suggesting a charge transfer process. The nanocomposites' chromaticity coordinates for CIE 1931 color space were estimated to be (0.33, 0.34), close to pure white ones. The obtained results highlight the possibility of using these nanocomposites to achieve good performance and suitability for optoelectronic applications.
RESUMEN
Epitaxial La0.67Ba0.33Ti0.02Mn0.98O3 (denoted as LBTMO hereafter) thin films of approximately 95 nm thickness were deposited by a pulsed laser deposition technique onto SrTiO3 (STO) (001) substrates. High-resolution X-ray diffraction (HRXRD) and transmission electron microscopy (TEM) investigations revealed that the films are epilayers with a four-fold symmetry around the [001] direction. Cross-sectional TEM and the presence of Pendellosung fringes in the XRD profiles demonstrate smooth interfaces. The STO substrate induces an in-plane compressive strain, which leads to a slight tetragonality of the film structure. The epilayers exhibit paramagnetic-to-ferromagnetic phase transitions at the Curie temperature TC (286 K), close to room temperature. The magnetization easy axis lies in the film plane along the [100] direction of the (001) substrate. The magnetic entropy change (ΔSM) associated with the second-order magnetic phase transition was determined via magnetization measurements in the temperature range between 210 and 350 K under different magnetic fields. The relative cooling power (RCP) of this film is about 220 J kg-1, somewhat lower than that of bulk Gd (410 J kg-1) for a 50 kOe field change, making the LBTMO ferromagnetic thin films a promising candidate for micro/nanomagnetic refrigeration around room temperature. The proposed universal curve provides a simple method for extrapolating ΔSM in a wide range of fields and temperatures, thus confirming the order of the magnetic transition in this system. The magnetic entropy (ΔSM)max around TC is proportional to (µ0H/TC)2/3 in agreement with the mean-field theory, indicating the existence of long-range ferromagnetic interactions in epitaxial LBTMO thin films.
