Colossal Permittivity Characteristics of (Nb,Si) Co-Doped TiO2 Ceramics

(Nb⁵⁺, Si⁴⁺) co-doped TiO₂ (NSTO) ceramics with the compositions (Nb_0.5Si_0.5)_xTi_1−xO₂, x = 0, 0.025, 0.050 and 0.1 were prepared with a solid-state reaction technique. X-ray diffraction (XRD) patterns and Raman spectra confirmed that the tetragonal rutile is the main phase in all the ceramics. Additionally, XRD revealed the presence of a secondary phase of SiO₂ in the co-doped ceramics. Impedance spectroscopy analysis showed two contributions, which correspond to the responses of grain and grain-boundary. All the (Nb, Si) co-doped TiO₂ showed improved dielectric performance in the high frequency range (>10³ Hz). The sample (Nb_0.5Si_0.5)_0.025Ti_0.975O₂ showed the best dielectric performance in terms of higher relative permittivity (5.5 × 10⁴) and lower dielectric loss (0.18), at 10 kHz and 300 K, compared to pure TiO₂ (1.1 × 10³, 0.34). The colossal permittivity of NSTO ceramics is attributed to an internal barrier layer capacitance (IBLC) effect, formed by insulating grain-boundaries and semiconductor grains in the ceramics.     

Crystal Growth and Spectroscopic Investigations of Tm3+:Li3Ba2Gd3(MoO4)8 Crystal

Tm³⁺:Li₃Ba₂Gd₃(MoO₄)₈ crystal has been grown by the top seeded solution growth (TSSG) method from a Li₂MoO₄ flux. The room temperature polarized absorption spectra, fluorescence spectra, and fluorescence decay curves of the crystal were measured. Based on the Judd-Ofelt (J-O) theory, the main spectroscopic parameters of the crystal, including the spontaneous emission probabilities, fluorescence branching ratios, and radiative lifetimes were calculated and analyzed. The broad and strong absorption bands of the crystal show that it can be efficiently pumped by the diode laser, while the large emission cross-sections of the ³F₄ → ³H₆ transition indicate that the crystal is a promising candidate for tunable and short pulse lasers.     

Cysteine-Induced Hybridization of 2D Molybdenum Disulfide Films for Efficient and Stable Hydrogen Evolution Reaction

The noble, metal-free materials capable of efficiently catalyzing water splitting reactions currently hold a great deal of promise. In this study, we reported the structure and electrochemical performance of new MoS₂-based material synthesized with L-cysteine. For this, a facile one-pot hydrothermal process was developed and an array of densely packed nanoplatelet-shaped hybrid species directly on a conductive substrate were obtained. The crucial role of L-cysteine was determined by numerous methods on the structure and composition of the synthesized material and its activity and stability for hydrogen evolution reaction (HER) from the acidic water. A low Tafel slope of 32.6 mV dec⁻¹, close to a Pt cathode, was registered for the first time. The unique HER performance at the surface of this hybrid material in comparison with recently reported MoS₂-based electrocatalysts was attributed to the formation of more defective 1T, 2H-MoS₂/MoO_x, C nanostructures with the dominant 1T-MoS₂ phase and thermally degraded cysteine residues entrapped. Numerous stacks of metallic (1T-MoS₂ and MoO₂) and semiconducting (2H-MoS₂ and MoO₃) fragments relayed the formation of highly active layered nanosheets possessing a low hydrogen adsorption free energy and much greater durability, whereas intercalated cysteine fragments had a low Tafel slope of the HER reaction. X-ray photoelectron spectroscopy, scanning electron microscopy, thermography with mass spectrometry, high-resolution transmission electron microscopy, Raman spectroscopy techniques, and linear sweep voltammetry were applied to verify our findings.     

Thermo-Exfoliated Graphite Containing CuO/Cu2(OH)3NO3:(Co2+/Fe3+) Composites: Preparation,Characterization and Catalytic Performance in CO Conversion

Thermo-exfoliated graphite (TEG)/CuO/Cu₂(OH)₃NO₃:(Co²⁺/Fe³⁺) composites were prepared using a wet impregnation method and subsequent thermal treatment. The physicochemical characterization of the composites was carried out by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and Ar temperature-desorption techniques. The catalytic efficiency toward CO conversion to CO₂ was examined under atmospheric pressure. Characterization of species adsorbed over the composites taken after the activity tests were performed by means of temperature programmed desorption mass-spectrometry (TPD MS). (TEG)/CuO/Cu₂(OH)₃NO₃:(Co²⁺/Fe³⁺) composites show superior performance results if lower temperatures and extra treatment with H₂SO₄ or HNO₃ are used at the preparation stages. The catalytic properties enhancements can be related to the Cu₂(OH)₃NO₃ phase providing reaction centers for the CO conversion. It has been found that prevalence of low-temperature states of desorbed CO₂ over high-temperature ones in the TPD MS spectra is characteristic of the most active composite catalysts.     

A Bio-Inspired Nanotubular Na2MoO4/TiO2 Composite as a High-Performance Anodic Material for Lithium-Ion Batteries

A train of bio-inspired nanotubular Na₂MoO₄/TiO₂ composites were synthesized by using a natural cellulose substance (e.g., commercial ordinary filter paper) as the structural template. The TiO₂ gel films were coated on the cellulose nanofiber surfaces via a sol-gel method firstly, followed with the deposition of the poly(diallyldimethylammonium chloride)/Na₂MoO₄ (PDDA/Na₂MoO₄) bi-layers several times, through the layer-by-layer self-assembly route, yielding the (PDDA/Na₂MoO₄)_n/TiO₂-gel/cellulose composite, which was calcined in air to give various Na₂MoO₄/TiO₂ nanocomposites containing different Na₂MoO₄ contents (15.4, 24.1, and 41.4%). The resultant nanocomposites all inherited the three-dimensionally porous network structure of the premier cellulose substance, which were formed by hierarchical TiO₂ nanotubes anchored with the Na₂MoO₄ layers. When employed as anodic materials for lithium-ion batteries, those Na₂MoO₄/TiO₂ nanocomposites exhibited promoted electrochemical performances in comparison with the Na₂MoO₄ powder and pure TiO₂ nanotubes, which was resulted from the high capacity of the Na₂MoO₄ component and the buffering effects of the TiO₂ nanotubes. Among all the nanotubular Na₂MoO₄/TiO₂ composites, the one with a Na₂MoO₄ content of 41.4% showed the best electrochemical properties, such as the cycling stability with a capacity of 180.22 mAh g⁻¹ after 200 charge/discharge cycles (current density: 100 mA g⁻¹) and the optimal rate capability.     

Molybdenum Oxide Nanoparticle Aggregates Grown by Chemical Vapor Transport

In this study, the advanced chemical vapor transport (CVT) method in combination with the quenching effect is introduced for creating molybdenum oxide nanoparticle arrays, composed of the hierarchical structure of fine nanoparticles (NPs), which are vertically grown with a homogeneous coverage on the individual carbon fibers of carbon fiber paper (CFP) substrates. The obtained molybdenum oxide NPs hold a metastable high-temperature γ-Mo₄O₁₁ phase along with a stable α-MoO₃ phase by the quenching effect. Furthermore, such a quenching effect forms thinner and smaller nanoparticle aggregates by suppressing the growth and coalescence of primary particles. The molybdenum oxide nanoparticle aggregates are prepared using two different types of precursors: MoO₃ and a 1:1 (mol/mol) mixture of MoO₃ and activated carbon. The results characterized using X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy show that the relative amount of α-MoO₃ to γ-Mo₄O₁₁ within the prepared NPs is dependent on the precursor type; a lower amount of α-MoO₃ to γ-Mo₄O₁₁ is obtained in the NPs prepared using the mixed precursor of MoO₃ and carbon. This processing–structure landscape study can serve as the groundwork for the development of high-performance nanomaterials in various electronic and catalytic applications.     

Storage of molecular hydrogen in an ammonia borane compound at high pressure

We studied ammonia borane (AB), NH₃BH₃, in the presence of excess hydrogen (H₂) pressure and discovered a solid phase, AB(H₂)_x, where x ≈1.3–2. The new AB–H₂ compound can store an estimated 8–12 wt % molecular H₂ in addition to the chemically bonded H₂ in AB. This phase formed slowly at 6.2 GPa, but the reaction rate could be enhanced by crushing the AB sample to increase its contact area with H₂. The compound has 2 Raman H₂ vibron peaks from the absorbed H₂ in this phase: one (ν₁) at frequency 70 cm⁻¹ below the free H₂ vibron, and the other (ν₂) at higher frequency overlapping with the free H₂ vibron at 6 GPa. The peaks shift linearly over the pressure interval of 6–16 GPa with average pressure coefficients of dν₁/dP = 4 cm⁻¹/GPa and dν₂/dP = 6 cm⁻¹/GPa. The formation of the compound is accompanied by changes in the N–H and B–H stretching Raman peaks resulting from the AB interactions with H₂ which indicate the structural complexity and low symmetry of this phase. Storage of significant amounts of additional molecular H₂ in AB increases the already high hydrogen content of AB, and may provide guidance for developing improved hydrogen storage materials.     

Praseodymium Orthoniobate and Praseodymium Substituted Lanthanum Orthoniobate: Electrical and Structural Properties

In this paper, the structural properties and the electrical conductivity of La_1−xPr_xNbO_4+δ (x = 0.00, 0.05, 0.1, 0.15, 0.2, 0.3) and PrNbO_4+δ are presented and discussed. All synthesized samples crystallized in a monoclinic structure with similar thermal expansion coefficients. The phase transition temperature between the monoclinic and tetragonal structure increases with increasing praseodymium content from 500 °C for undoped LaNbO_4+δ to 700 °C for PrNbO_4+δ. Thermogravimetry, along with X-ray photoelectron spectroscopy, confirmed a mixed 3⁺/4⁺ oxidation state of praseodymium. All studied materials, in humid air, exhibited mixed protonic, oxygen ionic and hole conductivity. The highest total conductivity was measured in dry air at 700 °C for PrNbO_4+δ, and its value was 1.4 × 10⁻³ S/cm.     

Exploring the Impact of Structure-Sensitivity Factors on Thermographic Properties of Dy3+-Doped Oxide Crystals

Optical absorption spectra and luminescence spectra were recorded as a function of temperature between 295 K and 800 K for single crystal samples of Gd₂SiO₅:Dy³⁺, Lu₂SiO₅:Dy³⁺, LiNbO₃:Dy³⁺, and Gd₃Ga₃Al₂O₁₂:Dy³⁺ fabricated by the Czochralski method and of YAl₃(BO₃)₄:Dy³⁺ fabricated by the top-seeded high temperature solution method. A thermally induced change of fluorescence intensity ratio (FIR) between the ⁴I_15/2→ ⁶H_15/2 and ⁴F_9/2 → ⁶H_15/2 emission bands of Dy³⁺ was inferred from experimental data. It was found that relative thermal sensitivities S_R at 350 K are higher for YAl₃(BO₃)₄:Dy³⁺ and Lu₂SiO₅:Dy³⁺than those for the remaining systems studied. Based on detailed examination of the structural peculiarities of the crystals it was ascertained that the observed difference between thermosensitive features cannot be attributed directly to the dissimilarity of structural factors consisting of the geometry and symmetry of Dy³⁺ sites, the number of non-equivalent Dy³⁺ sites, and the host anisotropy. Instead, it was found that a meaningful correlation between relative thermal sensitivity S_R and rates of radiative transitions of Dy³⁺ inferred from the Judd–Ofelt treatment exists. It was concluded that generalization based on the Judd–Ofelt parameters and luminescence branching ratio analysis may be useful during a preliminary assessment of thermosensitive properties of new phosphor materials.     

Structure and Photoluminescence Properties of Dy3+ Doped Phosphor with Whitlockite Structure

Whitlockite has the advantages of a low sintering temperature, high stability, and a low fabrication cost, and it is widely used as the host for luminescent material. In this study, Ca_1.8Li_0.6La_0.6−x(PO₄)₂:xDy³⁺ phosphor was prepared by the high-temperature solid-state method, and its structure, composition, and luminescence properties were systematically studied. The results showed that a new whitlockite type matrix was prepared by replacing Ca²⁺ in whitlockite with monovalent and trivalent cations. The prepared phosphors belonged to a hexagonal crystal system with a particle size in the range of 5–20 μm. Under the excitation of 350 nm UV light, the samples emitted white light, and there were mainly two stronger emission peaks at 481 nm in the blue band and 573 nm in the yellow band, which correspond to the electron transitions at ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The optimal doping concentration of Dy³⁺ in Ca_1.8Li_0.6La_0.6(PO₄)₂ matrix was 0.03 (mol%). The main mechanism of concentration quenching in the sample was dipole–dipole energy transfer. When the temperature was 130 °C, the luminescence intensity of the samples was 78.7% of that at 30 °C, and their thermal quenching activation energy was 0.25 eV. The CIE coordinates of the sample at 30 °C were (0.2750, 0.3006), and their luminescent colors do not change with temperature. All the results indicate that Ca_1.8Li_0.6La_0.6−x(PO₄)₂:xDy³⁺ phosphor is a luminescent material with good luminescence performance and thermal stability, which shows a promising application in the field of LED display.     

Humidity-Sensing Properties of an 1D Antiferromagnetic Oxalate-Bridged Coordination Polymer of Iron(III) and Its Temperature-Induced Structural Flexibility

A novel one-dimensional (1D) oxalate-bridged coordination polymer of iron(III), {[NH(CH₃)(C₂H₅)₂][FeCl₂(C₂O₄)]}_n (1), exhibits remarkable humidity-sensing properties and very high proton conductivity at room temperature (2.70 × 10⁻⁴ (Ω·cm)⁻¹ at 298 K under 93% relative humidity), in addition to the independent antiferromagnetic spin chains of iron(III) ions bridged by oxalate groups (J = −7.58(9) cm⁻¹). Moreover, the time-dependent measurements show that 1 could maintain a stable proton conductivity for at least 12 h. Charge transport and magnetic properties were investigated by impedance spectroscopy and magnetization measurements, respectively. Compound 1 consists of infinite anionic zig-zag chains [FeCl₂(C₂O₄)]_nⁿ⁻ and interposed diethylmethylammonium cations (C₂H₅)₂(CH₃)NH⁺, which act as hydrogen bond donors toward carbonyl oxygen atoms. Extraordinarily, the studied coordination polymer exhibits two reversible phase transitions: from the high-temperature phase HT to the mid-temperature phase MT at T ~213 K and from the mid-temperature phase MT to the low-temperature phase LT at T ~120 K, as revealed by in situ powder and single-crystal X-ray diffraction. All three polymorphs show large linear thermal expansion coefficients.     

Effect of Gd3+ Substitution on Thermoelectric Power Factor of Paramagnetic Co2+-Doped Calcium Molybdato-Tungstates

A series of Co²⁺-doped and Gd³⁺-co-doped calcium molybdato-tungstates, i.e., Ca_1−3x−yCo_{y x}Gd_2x(MoO₄)_1−3x(WO₄)_3x (CCGMWO), where 0 < x ≤ 0.2, y = 0.02 and represents vacancy, were successfully synthesized by high-temperature solid-state reaction method. XRD studies and diffuse reflectance UV–vis spectral analysis confirmed the formation of single, tetragonal scheelite-type phases with space group I4₁/a and a direct optical band gap above 3.5 eV. Magnetic and electrical measurements showed insulating behavior with n-type residual electrical conductivity, an almost perfect paramagnetic state with weak short-range ferromagnetic interactions, as well as an increase of spin contribution to the magnetic moment and an increase in the power factor with increasing gadolinium ions in the sample. Broadband dielectric spectroscopy measurements and dielectric analysis in the frequency representation showed a relatively high value of dielectric permittivity at low frequencies, characteristic of a space charge polarization and small values of both permittivity and loss tangent at higher frequencies.     

Temperature Dependence of Absorption and Energy Transfer Efficiency of Er3+/Yb3+/P5+ Co-Doped Silica Fiber Core Glasses

A high phosphorus Er³⁺/Yb³⁺ co-doped silica (EYPS) fiber core glass was prepared using the sol-gel method combined with high-temperature sintering. The absorption spectra, emission spectra, and fluorescence decay curves were measured and compared in temperatures ranging from 300 to 480 K. Compared to 915 and 97x nm, the absorption cross-section at ~940 nm (~0.173 pm²) demonstrates a weaker temperature dependence. Hence, the 940 nm pump mechanism is favorable for achieving a high-power laser output at 1.5 μm. Additionally, the double-exponential fluorescence decay of Yb³⁺ ions and the emission intensity ratio of I_1018nm/I_1534nm were measured to evaluate the energy transfer efficiency from Yb³⁺ ions to Er³⁺ ions. Through the external heating and active quantum defect heating methods, the emission intensity ratios of I_1018nm/I_1534nm increase by 30.6% and 709.1%, respectively, from ~300 to ~480 K. The results indicate that the temperature rises significantly reduce the efficiency of the energy transfer from the Yb³⁺ to the Er³⁺ ions.     

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.     

Enhanced Degradation of Rhodamine B by Metallic Organic Frameworks Based on NH2-MIL-125(Ti) under Visible Light

Samples of the bimetallic-based NH₂-MIL-125(Ti) at a ratio of Mⁿ⁺/Ti⁴⁺ is 0.15 (Mⁿ⁺: Ni²⁺, Co²⁺ and Fe³⁺) were first synthesized using the solvothermal method. Their fundamental properties were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectra, scanning electron microscopy (SEM), N₂ adsorption–desorption measurements, and UV–Vis diffuse reflectance spectroscopy (UV-Vis DRS). The as-acquired materials were used as high-efficiency heterogeneous photocatalysts to remove Rhodamine B (RhB) dye under visible light. The results verified that 82.4% of the RhB (3 × 10⁻⁵ M) was degraded within 120 min by 15% Fe/Ti−MOFs. Furthermore, in the purpose of degrading Rhodamine B (RhB), the rate constant for the 15% Fe/Ti-MOFs was found to be 2.6 times as fast as that of NH₂-MIL-125(Ti). Moreover, the 15% Fe/Ti-MOFs photocatalysts remained stable after three consecutive cycles. The trapping test demonstrated that the major active species in the degradation of the RhB process were hydroxyl radicals (HO^∙) and holes (h⁺).     

Effect of Heat Treatment on Structural,Magnetic and Electrical Properties of La2FeMnO6

In this study, the effect of heat treatment on the structural, magnetic and electrical properties of La₂FeMnO₆ prepared via the sol–gel and sintering method were investigated. The heat-treatment conditions, i.e., the calcination temperature (1023 K and 1173 K), sintering temperature and time (1273 K for 1 and 3 h) were carried out. X-ray diffraction (XRD) revealed orthorhombic pnma (62) symmetry without any impurity phase for all samples. X-ray photoelectron spectroscopy confirmed the presence of Fe²⁺–Fe³⁺–Fe⁴⁺ and Mn³⁺–Mn⁴⁺ mixed states, and lanthanum and oxygen vacancies resulting in various magnetic exchange interactions. Furthermore, the magnetisation hysteresis showed enhanced hysteresis loops accompanied by an increase in magnetisation parameters with calcination temperature. The Raman phonon parameters induced a redshift in the phonon modes, alongside an increase in the intensity and compression of the linewidth, reflecting a decrease in lattice distortion, which was confirmed by XRD. The temperature-dependent conductivity showed that the conduction mechanism is dominated by p-type polaron hopping, and the lowest activation energy was approximately 0.237 ± 0.003 eV for the minimum heat-treatment conditions. These results show that varying heat-treatment conditions can significantly affect the structural, magnetic and electrical properties of the La₂FeMnO₆ system.     

Crystal and Magnetic Structure Transitions in BiMnO3+δ Ceramics Driven by Cation Vacancies and Temperature

The crystal structure of BiMnO_3+δ ceramics has been studied as a function of nominal oxygen excess and temperature using synchrotron and neutron powder diffraction, magnetometry and differential scanning calorimetry. Increase in oxygen excess leads to the structural transformations from the monoclinic structure (C2/c) to another monoclinic (P2₁/c), and then to the orthorhombic (Pnma) structure through the two-phase regions. The sequence of the structural transformations is accompanied by a modification of the orbital ordering followed by its disruption. Modification of the orbital order leads to a rearrangement of the magnetic structure of the compounds from the long-range ferromagnetic to a mixed magnetic state with antiferromagnetic clusters coexistent in a ferromagnetic matrix followed by a frustration of the long-range magnetic order. Temperature increase causes the structural transition to the nonpolar orthorhombic phase regardless of the structural state at room temperature; the orbital order is destroyed in compounds BiMnO_3+δ (δ ≤ 0.14) at temperatures above 470 °C.     

Boost the Crystal Installation and Magnetic Features of Cobalt Ferrite/M-Type Strontium Ferrite Nanocomposites Double Substituted by La3+ and Sm3+ Ions (2CoFe2O4/SrFe12−2xSmxLaxO19)

Spinel cobalt ferrite/hexagonal strontium hexaferrite (2CoFe₂O₄/SrFe_12−2xSm_xLa_xO₁₉; x = 0.2, 0.5, 1.0, 1.5) nanocomposites were fabricated using the tartaric acid precursor pathway, and the effects of La³⁺–Sm³⁺ double substitution on the formation, structure, and magnetic properties of CoFe₂O₄/SrFe_12−2xSm_xLa_xO₁₉ nanocomposite at different annealing temperatures were assayed through X-ray diffraction, scanning electron microscopy, and vibrating sample magnetometry. A pure 2CoFe₂O₄/SrFe₁₂O₁₉ nanocomposite was obtained from the tartrate precursor complex annealed at 1100 °C for 2 h. The substitution of Fe³⁺ ion by Sm³–⁺La³⁺ions promoted the formation of pure 2CoFe₂O₄/SrFe₁₂O₁₉ nanocomposite at 1100 °C. The positions and intensities of the strongest peaks of hexagonal ferrite changed after Sm³⁺–La³⁺ substitution at ≤1100 °C. In addition, samples with an Sm³⁺–La³⁺ ratio of ≥1.0 annealed at 1200 °C for 2 h showed diffraction peaks for lanthanum cobalt oxide (La₃Co₃O₈; dominant phase) and samarium ferrite (SmFeO₃). The crystallite size range at all constituent phases was in the nanocrystalline range, from 39.4 nm to 122.4 nm. The average crystallite size of SrFe₁₂O₁₉ phase increased with the number of Sm³⁺–La³⁺ substitutions, whereas that of CoFe₂O₄ phase decreased with an x of up to 0.5. La–Sm co-doped ion substitution increased the saturation magnetization (Ms) value and the subrogated ratio to 0.2, and the Ms value decreased with the increasing number of double substitutions. A high saturation magnetization value (Ms = 69.6 emu/g) was obtained using a La³⁺–Sm³⁺ co-doped ratio of 0.2 at 1200 for 2 h, and a high coercive force value (Hc = 1192.0 Oe) was acquired using the same ratio at 1000 °C.     

Metal-Formate Framework Stiffening and Its Relevance to Phase Transition Mechanism

In the last decade, one of the most widely examined compounds of motal-organic frameworks was undoubtedly ((CH₃)₂NH₂)(Zn(HCOO)₃), but the problem of the importance of framework dynamics in the order–disorder phase change of the mechanism has not been fully clarified. In this study, a combination of temperature-dependent dielectric, calorimetric, IR, and Raman measurements was used to study the impact of ((CH₃)₂NH₂)(Zn(DCOO)₃) formate deuteration on the phase transition mechanism in this compound. This deuteration led to the stiffening of the metal-formate framework, which in turn caused an increase in the phase transition temperature by about 5 K. Interestingly, the energetic ordering of DMA⁺ cations remained unchanged compared to the non-deuterated compound.     

Structural and Luminescence Behavior of Nanocrystalline Orthophosphate KMeY(PO4)2: Eu3+ (Me = Ca,Sr) Synthesized by Hydrothermal Method

KMeY(PO₄)₂:5% Eu³⁺ phosphates have been synthesized by a novel hydrothermal method. Spectroscopic, structural, and morphological properties of the obtained samples were investigated by X-ray, TEM, Raman, infrared, absorption, and luminescence studies. The microscopic analysis of the obtained samples showed that the mean diameter of synthesized crystals was about 15 nm. The KCaY(PO₄)₂ and KSrY(PO₄)₂ compounds were isostructural and they crystallized in a rhabdophane-type hexagonal structure with the unit-cell parameters a = b ≈ 6.90 Å, c ≈ 6.34 Å, and a = b ≈ 7.00 Å, c ≈ 6.42 Å for the Ca and Sr compound, respectively. Spectroscopic investigations showed intense ⁵D₀ → ⁷F₄ transitions connected with D₂ site symmetry of Eu³⁺ ions. Furthermore, for the sample annealed at 500 °C, europium ions were located in two optical sites, on the surface of grains and in the bulk. Thermal treatment of powders at high temperature provided better grain crystallinity and only one position of dopant in the crystalline structure. The most intense emission was possessed by the KSrY(PO₄)₂:5% Eu³⁺ sample calcinated at 500 °C.