Micropowder Ca2YMgScSi3O12:Ce Silicate Garnet as an Efficient Light Converter for White LEDs

This work is dedicated to the crystallization and luminescent properties of a prospective Ca₂YMgScSi₃O₁₂:Ce (CYMSSG:Ce) micropowder (MP) phosphor converter (pc) for a white light–emitting LED (WLED). The set of MP samples was obtained by conventional solid-phase synthesis using different amounts of B₂O₃ flux in the 1–5 mole percentage range. The luminescent properties of the CYMSSG:Ce MPs were investigated at different Ce³⁺ concentrations in the 1–5 atomic percentage range. The formation of several Ce³⁺ multicenters in the CYMSSG:Ce MPs was detected in the emission and excitation spectra as well as the decay kinetics of the Ce³⁺ luminescence. The creation of the Ce³⁺ multicenters in CYMSSG:Ce garnet results from: (i) the substitution by the Ce³⁺ ions of the heterovalent Ca²⁺ and Y³⁺ cations in the dodecahedral position of the garnet host; (ii) the inhomogeneous local environment of the Ce³⁺ ions when the octahedral positions of the garnet are replaced by heterovalent Mg²⁺ and Sc³⁺ cations and the tetrahedral positions are replaced by Si⁴⁺ cations. The presence of Ce³⁺ multicenters significantly enhances the Ce³⁺ emission band in the red range in comparison with conventional YAG:Ce phosphor. Prototypes of the WLEDs were also created in this work by using CYMSSG:Ce MP films as phosphor converters. Furthermore, the dependence of the photoconversion properties on the layer thickness of the CYMSSG:Ce MP was studied as well. The changes in the MP layer thickness enable the tuning of the white light thons from cold white/daylight to neutral white. The obtained results are encouraging and can be useful for the development of a novel generation of pcs for WLEDs.     

Tunable Luminescence and Energy Transfer of Sr3B2O6:Ce3+, Sm3+ Phosphors with Potential Anti-Counterfeiting Applications

Sm³⁺ and Ce³⁺ singly doped and Sm³⁺ and Ce³⁺ co-doped Sr₃B₂O₆ phosphors are prepared via a high-temperature solid-state reaction method. The crystal structure and phase purity are characterized by X-ray diffraction (XRD) analyses. The Sm³⁺-doped sample displays an emission in the orange-red region, with the strongest emission line at about 648 nm and possessing a good luminescence thermal stability between 78 and 500 K. With the increase in the Sm³⁺ content, the concentration quenching is observed due to the cross-relaxation (CR) processes among the Sm³⁺ ions. Upon 340 nm excitation, the Ce³⁺-doped phosphor presents a broad emission band in the blue region with a maximum at about 420 nm, which overlaps well with the ⁶H_5/2 → ⁶P_3/2 excitation line of Sm³⁺ and implies the possible energy transfer from Ce³⁺ to Sm³⁺. The spectral and decay measurements of the Ce³⁺ and Sm³⁺ co-doped samples are conducted and the Inokuti–Hirayama (I-H) model is adopted to analyze the luminescence decay dynamics of the donor Ce³⁺. Owing to the evident sensitization of the Sm³⁺ by the Ce³⁺ ions, the co-doped samples exhibit color variation under different wavelength excitations, endowing them with potential applications in optical anti-counterfeiting.     

Structural and Photoluminescence Investigations of Tb3+/Eu3+ Co-Doped Silicate Sol-Gel Glass-Ceramics Containing CaF2 Nanocrystals

In this work, the series of Tb³⁺/Eu³⁺ co-doped xerogels and derivative glass-ceramics containing CaF₂ nanocrystals were prepared and characterized. The in situ formation of fluoride crystals was verified by an X-ray diffraction technique (XRD) and transmission electron microscopy (TEM). The studies of the Tb³⁺/Eu³⁺ energy transfer (ET) process were performed based on excitation and emission spectra along with luminescence decay analysis. According to emission spectra recorded under near-ultraviolet (NUV) excitation (351 nm, ⁷F₆ → ⁵L₉ transition of Tb³⁺), the mutual coexistence of the ⁵D₄ → ⁷F_J (J = 6–3) (Tb³⁺) and the ⁵D₀ → ⁷F_J (J = 0–4) (Eu³⁺) luminescence bands was clearly observed. The co-doping also resulted in gradual shortening of a lifetime from the ⁵D₄ state of Tb³⁺ ions, and the ET efficiencies were varied from η_ET = 11.9% (Tb³⁺:Eu³⁺ = 1:0.5) to η_ET = 22.9% (Tb³⁺:Eu³⁺ = 1:2) for xerogels, and from η_ET = 25.7% (Tb³⁺:Eu³⁺ = 1:0.5) up to η_ET = 67.4% (Tb³⁺:Eu³⁺ = 1:2) for glass-ceramics. Performed decay analysis from the ⁵D₀ (Eu³⁺) and the ⁵D₄ (Tb³⁺) state revealed a correlation with the change in Tb³⁺–Eu³⁺ and Eu³⁺–Eu³⁺ interionic distances resulting from both the variable Tb³⁺:Eu³⁺ molar ratio and their partial segregation in CaF₂ nanophase.     

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.     

A Novel Red-Emitting Na2NbOF5:Mn4+ Phosphor with Ultrahigh Color Purity for Warm White Lighting and Wide-Gamut Backlight Displays

In this work, a novel red-emitting oxyfluoride phosphor Na₂NbOF₅:Mn⁴⁺ with an ultra-intense zero-phonon line (ZPL) was successfully synthesized by hydrothermal method. The phase composition and luminescent properties of Na₂NbOF₅:Mn⁴⁺ were studied in detail. The photoluminescence excitation spectrum contains two intense excitation bands centered at 369 and 470 nm, which match well with commercial UV and blue light-emitting diode (LED) chips. When excited by 470 nm blue light, Na₂NbOF₅:Mn⁴⁺ exhibits red light emission dominated by ZPL. Notably, the color purity of the Na₂NbOF₅:Mn⁴⁺ red phosphor can reach 99.9%. Meanwhile, the Na₂NbOF₅:Mn⁴⁺ phosphor has a shorter fluorescence decay time than commercial K₂SiF₆:Mn⁴⁺, which is conducive to fast switching of images in display applications. Profiting from the intense ZPL, white light-emitting diode (WLED) with high color rendering index of Ra = 86.2 and low correlated color temperature of T_c = 3133 K is realized using yellow YAG:Ce³⁺ and red Na₂NbOF₅:Mn⁴⁺ phosphor. The WLED fabricated using CsPbBr₃ quantum dots (QDs) and red Na₂NbOF₅:Mn⁴⁺ phosphor shows a wide color gamut of 127.56% NTSC (National Television Standard Committee). The results show that red-emitting Na₂NbOF₅:Mn⁴⁺ phosphor has potential application prospects in WLED lighting and display backlight.     

Red-Emitting Hybrid Based on Eu3+-dbm Complex Anchored on Silica Nanoparticles Surface by Carboxylic Acid for Biomarker Application

Luminescent organic-inorganic hybrids containing lanthanides (Ln³⁺) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO₂) nanospheres decorated with Eu³⁺ β–diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO₂ surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu³⁺ to the carboxylate groups and (iv) coordination of dbm⁻ to Eu³⁺. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu³⁺-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of −27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu³⁺ complex provides intense red luminescence, characteristic of Eu^{3+ 5}D₀→⁷F_J electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging.     

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.     

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.     

Down-Shifting in the YAM: Ce3+ + Yb3+ System for Solar Cells

In this work, we investigate Ce³⁺ to Yb³⁺ energy transfer in Y₄Al₂O₉ (YAM) for potential application in solar spectrum down-converting layers for photovoltaic devices. Photoluminescence properties set, of 10 samples, of the YAM host activated with Ce³⁺ and Yb³⁺ with varying concentrations are presented, and the Ce³⁺ to Yb³⁺ energy transfer is proven. Measurement of highly non-exponential luminescence decays of Ce³⁺ 5d band allowed for the calculation of maximal theoretical quantum efficiency, of the expected down-conversion process, equal to 123%. Measurements of Yb³⁺ emission intensity, in the function of excitation power, confirmed the predominantly single-photon downshifting character of Ce³⁺ to Yb³⁺ energy transfer. Favorable location of the Ce³⁺ 5d bands in YAM makes this system a great candidate for down-converting, and down-shifting, luminescent layers for photovoltaics.     

Investigation of the TeO2/GeO2 Ratio on the Spectroscopic Properties of Eu3+-Doped Oxide Glasses for Optical Fiber Application

This study presented an analysis of the TeO₂/GeO₂ molar ratio in an oxide glass system. A family of melt-quenched glasses with the range of 0–35 mol% of GeO₂ has been characterized by using DSC, Raman, MIR, refractive index, PLE, PL spectra, and time-resolved spectral measurements. The increase in the content of germanium oxide caused an increase in the transition temperature but a decrease in the refractive index. The photoluminescence spectra of europium ions were examined under the excitation of 465 nm, corresponding to ⁷F₀ → ⁵D₂ transition. The PSB (phonon sidebands) analysis was carried out to determine the phonon energy of the glass hosts. It was reported that the red (⁵D₀ → ⁷F₂) to orange (⁵D₀ → ⁷F₁) fluorescence intensity ratio for Eu³⁺ ions decreased from 4.49 (Te0Ge) to 3.33 (Te15Ge) and showed a constant increase from 4.58 (Te20Ge) to 4.88 (Te35Ge). These optical features were explained in structural studies, especially changes in the coordination of ^[4]Ge to ^[6]Ge. The most extended lifetime was reported for the Eu³⁺ doped glass with the highest content of GeO₂. This glass was successfully used for the drawing of optical fiber.     

The Upconversion Luminescence of Er3+/Yb3+/Nd3+ Triply-Doped β-NaYF4 Nanocrystals under 808-nm Excitation

In this paper, Nd³⁺–Yb³⁺–Er³⁺-doped β-NaYF₄ nanocrystals with different Nd³⁺ concentrations are synthesized, and the luminescence properties of the upconversion nanoparticles (UCNPs) have been studied under 808-nm excitation for sensitive biological applications. The upconversion luminescence spectra of NaYF₄ nanoparticles with different dopants under 808-nm excitation proves that the Nd³⁺ ion can absorb the photons effectively, and the Yb³⁺ ion can play the role of an energy-transfer bridging ion between the Nd³⁺ ion and Er³⁺ ion. To investigate the effect of the Nd³⁺ ion, the decay curves of the ⁴S_3/2 → ⁴I_15/2 transition at 540 nm are measured and analyzed. The NaYF₄: 20% Yb³⁺, 2% Er³⁺, 0.5% Nd³⁺ nanocrystals have the highest emission intensity among all samples under 808-nm excitation. The UC (upconversion) mechanism under 808-nm excitation is discussed in terms of the experimental results.     

Synthesis and Characterization of Li2MgGeO4:Ho3+

In this work, the synthesis and characterization of Li₂MgGeO₄:Ho³⁺ ceramics were reported. The X-ray diffraction measurements revealed that the studied ceramics belong to the monoclinic Li₂MgGeO₄. Luminescence properties were analyzed in the visible spectral range. Green and red emission bands correspondent to the ⁵F₄,⁵S₂→⁵I₈ and ⁵F₅→⁵I₈ transitions of Ho³⁺ were observed, and their intensities were significantly dependent on activator concentration. Luminescence spectra were also measured under direct excitation of holmium ions or ceramic matrix. Holmium ions were inserted in crystal lattice Li₂MgGeO₄, giving broad blue emission and characteristic 4f-4f luminescent transitions of rare earths under the selective excitation of the ceramic matrix. The presence of the energy transfer process between the host lattice and Ho³⁺ ions was suggested.     

Phosphor Deposits of β-Sialon:Eu2+ Mixed with SnO2 Nanoparticles Fabricated by the Electrophoretic Deposition (EPD) Process

The phosphor deposits of the β-sialon:Eu²⁺ mixed with various amounts (0–1 g) of the SnO₂ nanoparticles were fabricated by the electrophoretic deposition (EPD) process. The mixed SnO₂ nanoparticles was observed to cover onto the particle surfaces of the β-sialon:Eu²⁺ as well as fill in the voids among the phosphor particles. The external and internal quantum efficiencies (QEs) of the prepared deposits were found to be dependent on the mixing amount of the SnO₂: by comparing with the deposit without any mixing (48% internal and 38% external QEs), after mixing the SnO₂ nanoparticles, the both QEs were improved to 55% internal and 43% external QEs at small mixing amount (0.05 g); whereas, with increasing the mixing amount to 0.1 and 1 g, they were reduced to 36% and 29% for the 0.1 g addition and 15% and 12% l QEs for the 1 g addition. More interestingly, tunable color appearances of the deposits prepared by the EPD process were achieved, from yellow green to blue, by varying the addition amount of the SnO₂, enabling it as an alternative technique instead of altering the voltage and depositing time for the color appearance controllability.     

Fabricated Flexible Composite for a UV-LED Color Filter and Anti-Counterfeiting Application of Calcium Molybdate Phosphor Synthesized at Room Temperature

Crystalline CaMoO₄ and rare-earth-doped CaMoO₄:RE³⁺ (RE = Tb, Eu) phosphors were synthesized at room temperature using a co-precipitation method. The crystal structure of the synthesized powder was a tetragonal structure with a main diffraction peak (112) phase. When CaMoO₄ was excited at 295 nm, it showed a central peak of 498 nm and light emission in a wide range of 420 to 700 nm. Rare-earth-ion-doped CaMoO₄:Tb³⁺ was excited at 288 nm and a green light emission was observed at 544 nm, and CaMoO₄:Eu³⁺ was excited at 292 nm and a red light emission was observed at 613 nm. To take advantage of the light-emitting characteristics, a flexible composite was manufactured and a color filter that could be used for UV-LEDs was manufactured. In addition, it was suggested that an ink that could be checked only by UV light could be produced and applied to banknotes so as to prevent counterfeiting.     

Wide Concentration Range of Tb3+ Doping Influence on Scintillation Properties of (Ce,Tb, Gd)3Ga2Al3O12 Crystals Grown by the Optical Floating Zone Method

To obtain a deeper understand of the energy transfer mechanism between Ce³⁺ and Tb³⁺ ions in the aluminum garnet hosts, (Ce, Tb, Gd)₃Ga₂Al₃O₁₂ (GGAG:Ce, Tb) single crystals grown by the optical floating zone (OFZ) method were investigated systematically in a wide range of Tb³⁺ doping concentration (1–66 at.%). Among those, crystal with 7 at.% Tb reached a single garnet phase while the crystals with other Tb³⁺ concentrations are mixed phases of garnet and perovskite. Obvious Ce and Ga loss can be observed by an energy dispersive X-ray spectroscope (EDS) technology. The absorption bands belonging to both Ce³⁺ and Tb³⁺ ions can be observed in all crystals. Photoluminescence (PL) spectra show the presence of an efficient energy transfer from the Tb³⁺ to Ce³⁺ and the gradually quenching effect with increasing of Tb³⁺ concentration. GGAG: 1% Ce³⁺, 7% Tb³⁺ crystal was found to possess the highest PL intensity under excitation of 450 nm. The maximum light yield (LY) reaches 18,941 pho/MeV. The improved luminescent and scintillation characteristics indicate that the cation engineering of Tb³⁺ can optimize the photoconversion performance of GGAG:Ce.     

Investigating the Impact of Cu2+ Doping on the Morphological,Structural, Optical,and Electrical Properties of CoFe2O4 Nanoparticles for Use in Electrical Devices

This study investigated the production of Cu²⁺-doped CoFe₂O₄ nanoparticles (CFO NPs) using a facile sol−gel technique. The impact of Cu²⁺ doping on the lattice parameters, morphology, optical properties, and electrical properties of CFO NPs was investigated for applications in electrical devices. The XRD analysis revealed the formation of spinel-phased crystalline structures of the specimens with no impurity phases. The average grain size, lattice constant, cell volume, and porosity were measured in the range of 4.55–7.07 nm, 8.1770–8.1097 Å, 546.7414–533.3525 ų, and 8.77–6.93%, respectively. The SEM analysis revealed a change in morphology of the specimens with a rise in Cu²⁺ content. The particles started gaining a defined shape and size with a rise in Cu²⁺ doping. The Cu_0.12Co_0.88Fe₂O₄ NPs revealed clear grain boundaries with the least agglomeration. The energy band gap declined from 3.98 eV to 3.21 eV with a shift in Cu²⁺ concentration from 0.4 to 0.12. The electrical studies showed that doping a trace amount of Cu²⁺ improved the electrical properties of the CFO NPs without producing any structural distortions. The conductivity of the Cu²⁺-doped CFO NPs increased from 6.66 × 10⁻¹⁰ to 5.26 × 10⁻⁶ ℧ cm⁻¹ with a rise in Cu²⁺ concentration. The improved structural and electrical characteristics of the prepared Cu²⁺-doped CFO NPs made them a suitable candidate for electrical devices, diodes, and sensor technology applications.     

The Effect of Fluorides (BaF2, MgF2, AlF3) on Structural and Luminescent Properties of Er3+-Doped Gallo-Germanate Glass

The effect of BaF₂, MgF₂, and AlF₃ on the structural and luminescent properties of gallo-germanate glass (BGG) doped with erbium ions was investigated. A detailed analysis of infrared and Raman spectra shows that the local environment of erbium ions in the glass was influenced mainly by [GeO]₄ and [GeO]₆ units. Moreover, the highest number of non-bridging oxygens was found in the network of the BGG glass modified by MgF₂. The ²⁷Al MAS NMR spectrum of BGG glass with AlF₃ suggests the presence of aluminum in tetra-, penta-, and octahedral coordination geometry. Therefore, the probability of the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ions increases in the BGG + MgF₂ glass system. On the other hand, the luminescence spectra showed that the fluoride modifiers lead to an enhancement in the emission of each analyzed transition when different excitation sources are employed (808 nm and 980 nm). The analysis of energy transfer mechanisms shows that the fluoride compounds promote the emission intensity in different channels. These results represent a strong base for designing glasses with unique luminescent properties.     

Activation of Connexin-43 Hemichannels Can Elevate [Ca]iand [Na]iin Rabbit Ventricular Myocytes During Metabolic Inhibition

ATP depletion due to ischemia or metabolic inhibition (MI) causes Na⁺and Ca²⁺accumulation in myocytes, which may be in part due to opening of connexin-43 hemichannels. Halothane (H) has been shown to reduce conductance of connexin-43 hemichannels and to protect the heart against ischemic injury. We therefore investigated the effect of halothane on [Ca²⁺]_iand [Na⁺]_iin myocytes during MI. Isolated rabbit left ventricular myocytes were loaded with 4μ m fluo-3 AM for 30 min, or with 5 μ m sodium green AM for 60 min at 37°C. After washing, the myocytes were exposed to: (1) Normal HEPES solution; (2) MI solution (2 m NaCN, 20 m 2-deoxy- -glucose and 0-glucose); or (3) MI+H (0.95 m , 4.7 m ) for 60 min. Propidium iodide (PI, 25 μ m) was added to all samples before data acquisition. The fluorescence intensity was measured by flow cytometry with 488 nm excitation and 530 nm emission for fluo-3 or sodium green, and 670 nm for PI. The [Ca²⁺]_iand [Na⁺]_iwere then calculated by calibration. In some experiments, the effect of 10 μ m tetrodotoxin (TTX) and 20 μ m nifedipine (NIF) were studied. Metabolic inhibition for 60 min caused a significant increase in [Ca²⁺]_iand [Na⁺]_iin myocytes when compared to controls, which was significantly reduced by halothane in a dose-dependent fashion. In the presence of TTX and NIF, halothane also significantly reduced the rise in the [Ca²⁺]_iand [Na⁺]_iin myocytes subjected to MI. 1-heptanol, another gap junction blocker, had similar effects. Thus, halothane reduced [Ca²⁺]_iand [Na⁺]_ioverload produced by MI in myocytes. This effect is not solely due to block of voltage-gated Na⁺and Ca²⁺channels, and is likely mediated by inhibiting the opening of connexin-43 hemichannels.     

Coordination of {Mo142} Ring to La3+ Provides Elliptical {Mo134La10} Ring with a Variety of Coordination Modes

A 28-electron reduced C_2h-Mo-blue 34Ǻ outer ring diameter circular ring, [Mo₁₄₂O₄₂₉H₁₀(H₂O)₄₉(CH₃CO₂)₅(C₂H₅CO₂)]^30- (≡{Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}) comprising eight carboxylate-coordinated (with disorder) {Mo₂} linkers and six defect pockets in two inner rings (four and three for each, respectively), reacts with La³⁺ in aqueous solutions at pH 3.5 to yield a 28-electron reduced elliptical C_i-Mo-blue ring of formula [Mo₁₃₄O₄₁₆H₂₀(H₂O)₄₆{La(H₂O)₅}₄{La(H₂O)₇}₄{LaCl₂(H₂O)₅}₂]^10- (≡{Mo₁₃₄La₁₀}), isolated as the Na₁₀[Mo₁₃₄O₄₁₆H₂₀(H₂O)₄₆{La(H₂O)₅}₄{La(H₂O)₇}₄{LaCl₂(H₂O)₅}₂]·144 H₂O Na⁺ salt. The elliptical structure of {Mo₁₃₄La₁₀} showing 36 and 31 Å long and short axes for the outer ring diameters is attributed to four (A-D) modes of LaO₉/LaO₇Cl₂ tricapped-trigonal-prismatic coordination (TTP) geometries. Two different LaO₂(H₂O)₇ and one LaO₂(H₂O)₂Cl₂ TTP geometries (as A-C modes) for each of two inner rings result from the coordination of all three defect pockets of the inner ring for {Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}, and two LaO₄(H₂O)₅ TTP geometries (as D mode) result from the displacement of two (acetate/propionate-coordinated) binuclear {Mo₂} linkers with La³⁺ in each inner ring. The isothermal titration calorimetry (ITC) of the ring modification from circle to ellipsoid, showing the endothermic reaction of [La³⁺]/[{Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}] = 6/1 with ΔH = 22 kJ⋅mol^-1, ΔS = 172 J⋅K^-1⋅mol^-1, ΔG = −28 kJ⋅mol^-1, and K = 9.9 × 10⁴ M^-1 at 293 K, leads to the conclusion that the coordination of the defect pockets to La³⁺ precedes the replacement of the {Mo₂} linkers with La³⁺. ¹³⁹La- NMR spectrometry of the coordination of {Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)} ring to La³⁺ is also discussed.     

Ultrasonic Spray Pyrolysis Synthesis and Photoluminescence of LuAG:Ce Thin Films

LuAG:Ce (Lu₃Al₅O₁₂:Ce) is one of the most important color converters in white lighting industry. Especially, LuAG:Ce film attracts more attention due to the outstanding advantages, such as the efficient heat dissipation, the saving of rare earth, and so on. Here, LuAG:Ce film on sapphire was successfully prepared by the ultrasonic spray pyrolysis process. The phase, microstructure and photoluminescence of LuAG:Ce films were investigated. LuAG:Ce films had a thickness of around 5 μm, which were well crystallized at 1000 °C in air atmosphere to form the typical garnet structure. Under the protection of CO atmosphere, increasing the annealing temperature greatly enhanced the photoluminescence performance. After annealing at 1500 °C for 5 h in CO atmosphere, 3.0 mol.% Ce³⁺ doped LuAG:Ce film exhibited the highest emission and excitation intensity. The emission intensity of 3.0 mol.% Ce³⁺ doped LuAG:Ce film annealed at 1500 °C in CO atmosphere increased up to five times, when compared with the best LuAG:Ce film annealed at 1000 °C in air atmosphere. The effects of Ce³⁺ doping concentration on the photoluminescence were also examined. As the Ce³⁺ doping concentration increased from 0.2 mol.% to 7.0 mol.%, the color of LuAG:Ce films changed from yellowish green to greenish yellow. When coupling the 3.0 mol.% Ce³⁺ doped LuAG:Ce film with a 0.5 W 450 nm blue laser, the formed device successfully emitted white light.