Role of Eu2+ and Dy3+ Concentration in the Persistent Luminescence of Sr2MgSi2O7 Glass-Ceramics

In this study, glass-ceramics based on Sr₂MgSi₂O₇ phosphor co-doped with Eu/Dy were obtained from the sintering and crystallisation of glass powders. The glasses were melted in a gas furnace to simulate an industrial process, and the dopant concentration was varied to optimise the luminescence persistence times. The doped parent glasses showed red emission under UV light excitation due to the doping of Eu³⁺ ions, while the corresponding glass-ceramics showed persistent blue emission corresponding to the presence of Eu²⁺ in the crystalline environment. The dopant concentration had a strong impact on the sintering/crystallisation kinetics affecting the final glass-ceramic microstructure. The microstructures and morphology of the crystals responsible for the blue emission were observed by scanning electron microscopy–cathodoluminescence. The composition of the crystallised phases and the distribution of rare-earth (RE) ions in the crystals and in the residual glassy phase were determined by X-ray diffraction and energy dispersive X-ray analysis. The emission and persistence of phosphorescence were studied by photoluminescence.     

The ZnO-In2O3 Oxide System as a Material for Low-Temperature Deposition of Transparent Electrodes

The development of optoelectronic devices based on flexible organic substrates substantially decreases the possible process temperatures during all stages of device manufacturing. This makes it urgent to search for new transparent conducting oxide (TCO) materials, cheaper than traditional indium-tin oxide (ITO), for the low-temperature deposition of transparent electrodes, a necessary component of most optoelectronic devices. The article presents the results of a vertically integrated study aimed at the low-temperature production of TCO thin films based on a zinc-indium oxide (ZIO) system with acceptable functional characteristics. First, dense and conducting ceramic targets based on the (100-x) mol% (ZnO) + x mol% (In₂O₃) system (x = 0.5, 1.5, 2.5, 5.0, and 10.0) were synthesized by the spark plasma sintering method. The dependences of the microstructure and phase composition of the ZIO ceramic targets on the In₂O₃ content have been studied by powder X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy methods. Then, a set of ZIO thin films with different Zn/In ratios were obtained on unheated glass substrates by direct current (dc) magnetron sputtering of the sintered targets. Complex studies of microstructure, electrical and optical properties of the deposited films have revealed the presence of an optimal doping level (5 mol% In₂O₃) of the ZIO target at which the deposited TCO films, in terms of the combination of their electrical and optical properties, become comparable to the widely used expensive ITO.     

Effect of Annealing Temperature and Oxygen Flow in the Properties of Ion Beam Sputtered SnO2?x Thin Films

Tin oxide (SnO_2−x) thin films were prepared under various flow ratios of O₂/(O₂ + Ar) on unheated glass substrate using the ion beam sputtering (IBS) deposition technique. This work studied the effects of the flow ratio of O₂/(O₂ + Ar), chamber pressures and post-annealing treatment on the physical properties of SnO₂ thin films. It was found that annealing affects the crystal quality of the films as seen from both X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. In addition, the surface RMS roughness was measured with atomic force microscopy (AFM). Auger electron spectroscopy (AES) analysis was used to obtain the changes of elemental distribution between tin and oxygen atomic concentration. The electrical property is discussed with attention to the structure factor.     

Flexible Sol-Gel—Processed Y2O3 RRAM Devices Obtained via UV/Ozone-Assisted Photochemical Annealing Process

Flexible indium tin oxide (ITO)/Y₂O₃/Ag resistive random access memory (RRAM) devices were successfully fabricated using a thermal-energy-free ultraviolet (UV)/ozone-assisted photochemical annealing process. Using the UV/ozone-assisted photochemical process, the organic residue can be eliminated, and thinner and smother Y₂O₃ films than those formed using other methods can be fabricated. The flexible UV/ozone-assisted photochemical annealing process-based ITO/Y₂O₃/Ag RRAM devices exhibited the properties of conventional bipolar RRAM without any forming process. Furthermore, the pure and amorphous-phase Y₂O₃ films formed via this process showed a decreased leakage current and an increased high-resistance status (HRS) compared with the films formed using other methods. Therefore, RRAM devices can be realized on plastic substrates using a thermal-energy-free UV/ozone-assisted photochemical annealing process. The fabricated devices exhibited a resistive window (ratio of HRS/low-resistance status (LRS)) of >10⁴, with the HRS and LRS values remaining almost the same (i.e., limited deterioration occurred) for 10⁴ s and up to 10² programming/erasing operation cycles.     

Enhanced Switching Reliability of Sol–Gel-Processed Y2O3 RRAM Devices Based on Y2O3 Surface Roughness-Induced Local Electric Field

Sol–gel-processed Y₂O₃ films were used as active channel layers for resistive random access memory (RRAM) devices. The fabricated ITO/Y₂O₃/Ag RRAM devices exhibited the properties of conventional bipolar memory devices. A triethylamine stabilizer with a high vapor pressure and low surface tension was added to realize the local electric field area. During drying and high-temperature post-annealing processes, the large convective flow enhanced the surface elevation, and the increased –OH groups accelerated the hydrolysis reaction and aggregation. These phenomena afforded Y₂O₃ films with an uneven surface morphology and an increased surface roughness. The increased roughness of the Y₂O₃ films attributable to the triethylamine stabilizer enhanced the local electrical field, improved device reliability, and achieved successful repetition of the switching properties over an extended period.     

Drop–Dry Deposition of Ni(OH)2 Precursors for Fabrication of NiO Thin Films

Drop–dry deposition (DDD) is a method of depositing thin films by heating and drying the deposition solution dropped on a substrate. We prepared Ni(OH)₂ precursor thin films by DDD and annealed them in air to prepare NiO thin films. The appropriate deposition conditions were found by changing the number of drop–dry cycles and the concentrations of chemicals in the solution, and the Ni(OH)₂ precursor film with a thickness of 0.3 μm and optical transmittance of more than 95% was successfully deposited. Raman and X-ray diffraction measurements were performed, and it was found that the NiO film was successfully fabricated after annealing at 400 °C. The p-type conductivity of the annealed film was confirmed by photoelectrochemical measurements. In addition, we prepared n-type ZnO by electrochemical deposition on NiO thin films. The current–voltage measurement results show that the ZnO/NiO heterojunction had rectification properties.     

Tuning of Emission Wavelength of CaS:Eu by Addition of Oxygen Using Atomic Layer Deposition

Atomic layer deposition (ALD) technology has unlocked new ways of manipulating the growth of inorganic materials. The fine control at the atomic level allowed by ALD technology creates the perfect conditions for the inclusion of new cationic or anionic elements of the already-known materials. Consequently, novel material characteristics may arise with new functions for applications. This is especially relevant for inorganic luminescent materials where slight changes in the vicinity of the luminescent centers may originate new emission properties. Here, we studied the luminescent properties of CaS:Eu by introducing europium with oxygen ions by ALD, resulting in a novel CaS:EuO thin film. We study structural and photoluminescent properties of two different ALD deposited Eu doped CaS thin films: Eu(thd)₃ which reacted with H₂S forming CaS:Eu phosphor, or with O₃ originating a CaS:EuO phosphor. It was found that the emission wavelength of CaS:EuO was 625.8 nm whereas CaS:Eu was 647 nm. Thus, the inclusion of O²⁻ ions by ALD in a CaS:Eu phosphor results in the blue-shift of 21.2 nm. Our results show that ALD can be an effective way to introduce additional elements (e.g., anionic elements) to engineer the physical properties (e.g., inorganic phosphor emissions) for photonics and optoelectronics.     

Molybdenum Oxide Thin Films Grown on Flexible ITO-Coated PET Substrates

Molybdenum oxide thin films were deposited on stiff and flexible substrates by reactive DC magnetron sputtering. Two sets of samples were prepared. The first with different O₂/Ar flow rate ratios and the second, fixing the oxygen content, with different time of deposition. As the O₂/Ar flow rate ratio varies from 0 up to 0.56, a threshold was found, ranging from crystalline to amorphous nature, and from a nontransparent appearance with metallic-like electrical conductivity to transparent and dielectric behaviour. From the second set, all transparent, the MoO_x films present a compact/dense and featureless morphology with thickness from 190 up to 910 nm, depending on the time of deposition. Their structure was corroborated by XPS and Rutherford Backscattering Spectrometry (RBS) and density measurements were performed by RBS and X-ray reflectivity (XRR), revealing a value of 2.4 g/cm³. The surface roughness is in the order of a few nanometers and the maxima optical transmission, in the visible range, is around 89%. Electrochemical cyclic voltammograms showed noticeable color reversibility and reproducibility on the flexible substrates opening new framework possibilities for new electrochomic devices.     

Phenomena Occurring upon the Sintering of a Mixture of Yttria–Zirconia Nanometric Powder and Sub-Micrometric Pure Zirconia Powder

Mixtures of powders essentially differing in their particle morphology and size were applied to prepare polycrystals in a Y₂O₃-ZrO₂ system. An yttria–zirconia solid solution nanometric powder with a Y₂O₃ concentration of 3.5% was prepared by subjecting co-precipitated gels to hydrothermal treatment at 240 °C. The crystallization occurred in distilled water. The pure zirconia powders composed of elongated and sub-micrometer size particles were also manufactured through the hydrothermal treatment of pure zirconia gel, although in this case, the process took place in the NaOH solution. Mixtures of the two kinds of powder were prepared so as to produce a mean composition corresponding to an yttria concentration of 3 mol%. Compacts of this powder mixture were sintered, and changes in phase composition vs. temperature were studied using X-ray diffraction. The dilatometry measurements revealed the behavior of the powder compact during sintering. The polished surfaces revealed the microstructure of the resulting polycrystal. Additionally, the electron back scattering diffraction technique (EBSD) allowed us to identify symmetry between the observed grains. Hardness, fracture toughness, and mechanical strength measurements were also performed.     

In Situ Hall Effect Monitoring of Vacuum Annealing of In2O3:H Thin Films

Hydrogen doped In₂O₃ thin films were prepared by room temperature sputter deposition with the addition of H₂O to the sputter gas. By subsequent vacuum annealing, the films obtain high mobility up to 90 cm²/Vs. The films were analyzed in situ by X-ray photoelectron spectroscopy (XPS) and ex situ by X-ray diffraction (XRD), optical transmission and Hall effect measurements. Furthermore, we present results from in situ Hall effect measurements during vacuum annealing of In₂O₃:H films, revealing distinct dependence of carrier concentration and mobility with time at different annealing temperatures. We suggest hydrogen passivation of grain boundaries as the main reason for the high mobility obtained with In₂O₃:H films.     

Structural and Luminescence Properties of Lu2O3:Eu3+ F127 Tri-Block Copolymer Modified Thin Films Prepared by Sol-Gel Method

Lu₂O₃:Eu³⁺ transparent, high density, and optical quality thin films were prepared using the sol-gel dip-coating technique, starting with lutetium and europium nitrates as precursors and followed by hydrolysis in an ethanol-ethylene glycol solution. Acetic acid and acetylacetonate were incorporated in order to adjust pH and as a sol stabilizer. In order to increment the thickness of the films and orient the structure, F127 Pluronic acid was incorporated during the sol formation. Structural, morphological, and optical properties of the films were investigated for different F127/Lu molar ratios (0–5) in order to obtain high optical quality films with enhanced thickness compared with the traditional method. X-ray diffraction (XRD) shows that the films present a highly oriented cubic structure <111> beyond 1073 K for a 3-layer film, on silica glass substrates. The thickness, density, porosity, and refractive index evolution of the films were investigated by means of m-lines microscopy along with the morphology by scanning electron microscope (SEM) and luminescent properties.     

Thermal Annealing Effects of V2O5 Thin Film as an Ionic Storage Layer for Electrochromic Application

A vanadium pentoxide (V₂O₅) thin film with thermal annealing as an ionic storage layer for electrochromic devices is presented in our study. The V₂O₅ thin film was deposited on an ITO glass substrate by an RF magnetron sputtering. The electrochromic properties of the film were evaluated after various thermal annealing temperatures. The structural analysis of the film was observed by X-ray diffraction (XRD), field emission electron microscopy (FE-SEM), and atomic force microscopy (AFM). The structure of the V₂O₅ thin film transformed from an amorphous to polycrystalline structure with directions of (110) and (020) after 400 °C thermal annealing. The electrochromic properties of the film improved compared with the unannealed V₂O₅ thin film. We obtained a charge capacity of 97.9 mC/cm² with a transparent difference ΔT value of 31% and coloration efficiency of 6.3 cm²/C after 400 °C thermal annealing. The improvement was due to the polycrystalline orthorhombic structure formation of V₂O₅ film by the rearrangement of atoms from thermal energy. Its laminate structure facilitates Li⁺ ion intercalation and increases charge capacity and transparent difference.     

Structural Features of Y2O2SO4 via DFT Calculations of Electronic and Vibrational Properties

The traditional way for determination of molecular groups structure in crystals is the X-Ray diffraction analysis and it is based on an estimation of the interatomic distances. Here, we report the analysis of structural units in Y₂O₂SO₄ using density functional theory calculations of electronic properties, lattice dynamics and experimental vibrational spectroscopy. The Y₂O₂SO₄ powder was successfully synthesized by decomposition of Y₂(SO₄)₃ at high temperature. According to the electronic band structure calculations, yttrium oxysulfate is a dielectric material. The difference between the oxygen–sulfur and oxygen–yttrium bond nature in Y₂O₂OS₄ was shown based on partial density of states calculations. Vibrational modes of sulfur ions and [Y₂O₂²⁺] chains were obtained theoretically and corresponding spectral lines observed in experimental Infrared and Raman spectra.     

Intrinsic Properties of Multi-Layer TiO2/V2O5/TiO2 Coatings Prepared via E-Beam Evaporation

Nanocomposite multi-layer TiO₂/V₂O₅/TiO₂ thin films were prepared via electron-beam evaporation using high-purity targets (TiO₂ and V₂O₅ purity > 99.9%) at substrate temperatures of 270 °C (TiO₂) and 25 °C (V₂O₅) under a partial pressure of oxygen of 2 × 10⁻⁴ mbar to maintain the stoichiometry. Rutherford backscattering spectrometry was used to confirm the layer structure and the optimal stoichiometry of the thin films, with a particle size of 20 to 40 nm. The thin films showed an optical transmittance of ~78% in the visible region and a reflectance of ~90% in the infrared. A decrease in transmittance was observed due to the greater cumulative thickness of the three layers and multiple reflections at the interface of the layers. The optical bandgap of the TiO₂ mono-layer was ~3.49 eV, whereas that of the multi-layer TiO₂/V₂O₅/TiO₂ reached ~3.51 eV. The increase in the optical bandgap was due to the inter-diffusion of the layers at an elevated substrate temperature during the deposition. The intrinsic, structural, and morphological features of the TiO₂/V₂O₅/TiO₂ thin films suggest their efficient use as a solar water heater system.     

Quasi-Continuous Network Structure Greatly Improved the Anti-Arc-Erosion Capability of Ag/Y2O3 Electrical Contacts

Ag/Y₂O₃ has excellent potential to replace Ag/CdO as the environmentally friendly electrical contact material. Using spherical Y₂O₃ as the starting material, Ag/Y₂O₃ contacts with a quasi-continuous network structure were successfully fabricated by a low-energy ball milling treatment. The mean size of Y₂O₃ used ranged from 243 to 980 nm. Due to the differences in the size of Y₂O₃, Ag/Y₂O₃ contacts had different primitive microstructures, thereby exhibiting distinctive anti-arc-erosion capabilities. Ag/Y₂O₃ contact prepared using 243 nm Y₂O₃ showed the best anti-arc-erosion capability and the most outstanding electrical performance measures, such as low contact resistance, less mass transfer, and no failure up to 10⁵ cycle times. The quasi-continuous network structure formed in the micro-scale was responsible for the excellent electrical performance. The short distance between Y₂O₃ particles in the network promoted the cathode arc motion, and thus alleviated the localized erosion. The results obtained herein may inspire further attempts to design electrical contacts rationally.     

Combustion Synthesis and Photoluminescence Properties of Red-Emitting CaAlSiN3:Eu2+ Phosphor for White-LEDs

A combustion synthesis method has been developed for synthesis of Eu²⁺ doped CaAlSiN₃ phosphor and its photoluminescence properties were investigated. Ca, Al, Si, and Eu₂O₃ powders were used as the Ca, Al, Si and Eu sources. The addition of NaN₃, NH₄Cl and Si₃N₄ powders was found to increase significantly the product yield. These powders were mixed and pressed into a compact, which was then wrapped up with an igniting agent (i.e., Mg+Fe₃O₄). The compact was ignited by electrical heating under a N₂ pressure of ≤1.0 MPa. Effects of these experimental parameters on the product yield were investigated and a reaction mechanism was proposed. The synthesized CaAlSiN₃:Eu²⁺ phosphor absorbs light in the region of 200–600 nm and shows a broad band emission in the region of 500–800 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. The sample doped with Eu²⁺ at the optimized molar ratio of 0.04 is efficiently excited by the blue light (460 nm) and generates emission peaking at ~650 nm with peak emission intensity ~106% of a commercially available phosphor, YAG:Ce³⁺(P46-Y3).The internal quantum efficiency of the synthesized phosphor was measured to be 71%, compared to 69% of the YAG:Ce³⁺ (P46-Y3).     

Sol-Gel Synthesis and Antioxidant Properties of Yttrium Oxide Nanocrystallites Incorporating P-123

Yttrium oxide (Y₂O₃) nanocrystallites were synthesized by mean of a sol-gel method using two different precursors. Raw materials used were yttrium nitrate and yttrium chloride, in methanol. In order to promote oxygen vacancies, P-123 poloxamer was incorporated. Synthesized systems were heat-treated at temperatures from 700 °C to 900 °C. Systems at 900 °C were prepared in the presence and absence of P-123 using different molar ratios (P-123:Y = 1:1 and 2:1). Fourier transform infrared spectroscopy (FTIR) results revealed a characteristic absorption band of Y–O vibrations typical of Y₂O₃ matrix. The structural phase was analyzed by X-ray diffraction (XRD), showing the characteristic cubic phase in all systems. The diffraction peak that presented the major intensity corresponded to the sample prepared from yttrium chloride incorporating P-123 in a molar ratio of P-123:Y = 2:1 at 900 °C. Crystallites sizes were determined by Scherrer equation as between 21 nm and 32 nm. Antioxidant properties were estimated by 2,2-diphenyl-1-picrylhydrazyl (DPPH•) assays; the results are discussed.     

Surface Characterization and Photoluminescence Properties of Ce3+,Eu Co-Doped SrF2 Nanophosphor

SrF₂:Eu,Ce³⁺ nanophosphors were successfully synthesized by the hydrothermal method during down-shifting investigations for solar cell applications. The phosphors were characterized by X-ray diffraction (XRD), scanning Auger nanoprobe, time of flight-secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. XRD showed that the crystallite size calculated with Scherrer’s equation was in the nanometre scale. XPS confirmed the formation of the matrix and the presence of the dopants in the SrF₂ host. The PL of the nanophosphor samples were studied using different excitation sources. The phenomenon of energy transfer from Ce³⁺ to Eu²⁺ has been demonstrated.     

Study of the Layer-Type BST Thin Film with X-ray Diffraction and X-ray Photoelectron Spectroscopy

In the present paper, results of X-ray photoelectron studies of electroceramic thin films of barium strontium titanate, Ba_1−xSr_xTiO₃ (BST), composition deposited on stainless-steel substrates are presented. The thin films were prepared by the sol-gel method. A spin-coating deposition of BST layers with different chemical compositions was utilized so the layer-type structure of (0-2) connectivity was formed. After the deposition, the thin-film samples were heated in air atmosphere at temperature T = 700 °C for 1 h. The surfaces of BST thin films subjected to thermal treatment were studied by X-ray diffraction. X-ray diffraction measurements confirmed the perovskite-type phase for all grown thin-film samples. The oxidation states of the elements were examined by the X-ray photoelectron spectroscopy method. X-ray photoelectron spectroscopy survey spectra as well as high-resolution spectra (photo-peaks) of the main metallic elements, such as Ti, Ba, and Sr, were compared for the layer-type structures, differing in the deposition sequence of the barium strontium titanate layers constituting the BST thin film.     

Mechanical Properties of Cu2O Thin Films by Nanoindentation

In this study, the structural and nanomechanical properties of Cu₂O thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and nanoindentation techniques. The Cu₂O thin films are deposited on the glass substrates with the various growth temperatures of 150, 250 and 350 °C by using radio frequency magnetron sputtering. The XRD results show that Cu₂O thin films are predominant (111)-oriented, indicating a well ordered microstructure. In addition, the hardness and Young’s modulus of Cu₂O thin films are measured by using a Berkovich nanoindenter operated with the continuous contact stiffness measurements (CSM) option. Results indicated that the hardness and Young’s modulus of Cu₂O thin films decreased as the growth temperature increased from 150 to 350 °C. Furthermore, the relationship between the hardness and films grain size appears to closely follow the Hall-Petch equation.