Bright Transparent Scintillators with High Fraction BaCl2 : Eu2+ Nanocrystals Precipitation: An Ionic-Covalent Hybrid Network Strategy toward Superior X-Ray Imaging Glass-Ceramics.

Metal halide crystals are bright but hygroscopic scintillator materials that are widely used in X-ray imaging and detectors. Precipitating them in situ in glass to form glass ceramics (GCs) scintillator offers an efficient avenue for large-scale preparation, high spatial resolution, and excellent stability. However, precipitating a high fraction of metal halide nanocrystals in glass to maintain high light yield remains a challenge. Herein, an ionic-covalent hybrid network strategy for constructing GCs scintillator with high crystallinity (up to ≈37%) of BaCl2 : Eu2+ nanocrystals is presented. Experimental data and simulations of glass structure reveal that the Ba2+ -Cl- clustering promotes the high crystallization of BaCl2 nanocrystals. The ultralow phonon energy (≈200 cm-1 ) of BaCl2 nanocrystals and good Eu reduction effect enable high photoluminescence inter quantum efficiency (≈80.41%) in GC. GCs with varied crystallinity of BaCl2 : Eu2+ nanocrystals demonstrate efficient radioluminescence and tunable scintillator performance. They either outperform Bi4 Ge3 O14 single crystal by over 132% steady-state light yield or provide impressive X-ray imaging resolutions of 20 lp mm-1 . These findings provide a new design strategy for developing bright transparent GCs scintillators with a high fraction of metal halide nanocrystals for X-ray high-resolution imaging applications.

Band Gap and Defect Engineering Enhanced Scintillation from Ce3+-Doped Nanoglass Containing Mixed-Type Fluoride Nanocrystals.

Much can be learned from the research and development of scintillator crystals for improving the scintillation performance of glasses. Relying on the concept of "embedding crystalline order in glass", we have demonstrated that the scintillation properties of Ce3+-doped nanoglass composites (nano-GCs) can be optimized via the synergistic effects of Gd3+-sublattice sensitization and band-gap engineering. The nano-GCs host a large volume fraction of KYxGd1-xF4 mixed-type fluoride nanocrystals (NCs) and still retain reasonably good transparency at Ce3+-emitting wavelengths. The light yield of 3455 ± 20 ph/MeV is found, which is the largest value ever reported in fluoride NC-embedded nano-GCs. A comprehensive study is given on the highly selective doping of Ce3+ in the NCs and its positive effect on the scintillation properties. The favorable influence of the Y3+/Gd3+ mixing on the suppression of defects is accounted for by density functional theory and borne out experimentally. As a proof-of-concept, X-ray imaging with a good spatial resolution (7.9 lp/mm) is demonstrated by employing Ce3+-doped nano-GCs. The superior radiation hardness, repeatability, and thermal stability of the designed scintillators bode well for their long-term practical applications.

Rapid determination of serum amyloid A using an upconversion luminescent lateral flow immunochromatographic strip.

The early diagnosis and real-time prognosis of cardiovascular diseases (CVDs) at the bedside are important. However, real-time detection of myocardial infarction involves the use of large-scale instrumentation and long test times. Herein, a simple, rapid and sensitive lateral flow immunochromatographic strip (LFIS) based on Yb/Er co-doped NaYF4 upconversion nanoparticles (UCNPs) was demonstrated for use in the detection of myocardial infarction. First, through heavy Yb/Er doping and an inert NaYF4 shell coating on the nanoparticles, the surface-related luminescence quenching effect of UCNPs was eliminated to enhance the upconversion luminescence. Second, through uniform coating of a SiO2 layer on the UCNPs, the biological affinity was improved to couple UCNPs and antibody proteins. Finally, through modification and activation with a specific antibody protein (serum amyloid A (SAA)), the UCNPs exhibited intense upconversion luminescence and high specificity when applied as a lateral flow immunochromatographic strip (LFIS). The developed UC-LFIS was highly sensitive (0.1 µg mL-1) and specific for detecting SAA in only 10 µL of serum. The UC-LFIS holds great potential for the early diagnosis and prognosis of CVDs.

Reversible Growth of Halide Perovskites via Lead Oxide Hydroxide Nitrates Anchored Zeolitic Imidazolate Frameworks for Information Encryption and Decryption.

The low formation energies of metal halide perovskites endow them with potential luminescent materials for applications in information encryption and decryption. However, reversible encryption and decryption are greatly hindered by the difficulty in robustly integrating perovskite ingredients into carrier materials. Here, we report an effective strategy to realize information encryption and decryption by reversible synthesis of halide perovskites, on the lead oxide hydroxide nitrates (Pb13O8(OH)6(NO3)4) anchored zeolitic imidazolate framework composites. Benefiting from the superior stability of ZIF-8 in combination with the strong bond between Pb and N evidenced by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy, the as-prepared Pb13O8(OH)6(NO3)4-ZIF-8 nanocomposites (Pb-ZIF-8) can withstand common polar solvent attack. Taking advantage of blade-coating and laser etching, the Pb-ZIF-8 confidential films can be readily encrypted and subsequently decrypted through reaction with halide ammonium salt. Consequently, multiple cycles of encryption and decryption are realized by quenching and recovery of the luminescent MAPbBr3-ZIF-8 films with polar solvents vapor and MABr reaction, respectively. These results provide a viable approach to integrate the state-of-the-art materials perovskites and ZIF for applications in information encryption and decryption films with large scale (up to 6 × 6 cm2), flexibility, and high resolution (approximate 5 µm line width).

Hybridization Engineering of Oxyfluoride Aluminosilicate Glass for Construction of Dual-Phase Optical Ceramics.

The construction of transparent ceramics under mild conditionsand standard atmospheric pressure has great scientific and technological potential; however, it remains difficult to achieve when conventional ceramic sintering techniques are used. Herein, a mild strategy for constructing dual-phase optical ceramics with high crystallinity (>90%) based on the stepped dual-phase crystallization of hybridized aluminosilicate glass is presented. Theoretical and experimental studies reveal that the hybridization of the glass system enables a new balance between the glass-forming ability and crystallization and can overcome the uncontrolled devitrification phenomenon during the dense crystallization of glass. Transparent hybridized oxide-fluoride ceramics with fiber geometry and dual-phase microstructures are also successfully fabricated. The generality of the strategy is confirmed, and transparent ceramics with various chemical compositions and phase combinations are prepared. Additionally, the cross-section of the ceramic fibers can be easily tuned into a circle, square, trapezoid, or even a triangle. Furthermore, the practical applications of optical ceramics for lighting and X-ray imaging are demonstrated. The findings described here suggest a major step toward expanding the scope of optical ceramics.

Neuromorphic device based on silicon nanosheets.

Silicon is vital for its high abundance, vast production, and perfect compatibility with the well-established CMOS processing industry. Recently, artificially stacked layered 2D structures have gained tremendous attention via fine-tuning properties for electronic devices. This article presents neuromorphic devices based on silicon nanosheets that are chemically exfoliated and surface-modified, enabling self-assembly into hierarchical stacking structures. The device functionality can be switched between a unipolar memristor and a feasibly reset-able synaptic device. The memory function of the device is based on the charge storage in the partially oxidized SiNS stacks followed by the discharge activated by the electric field at the Au-Si Schottky interface, as verified in both experimental and theoretical means. This work further inspired elegant neuromorphic computation models for digit recognition and noise filtration. Ultimately, it brings silicon - the most established semiconductor - back to the forefront for next-generation computations.

A modified random network model for P2O5-Na2O-Al2O3-SiO2 glass studied by molecular dynamics simulations.

We investigated the short- and medium-range structural features of sodium aluminosilicate glasses with various P2O5 (0-7 mol%) content and Al/Na ratios ranging from 0.667 to 2.000 by using molecular dynamics simulations. The local environment evolution of network former cations (Si, Al, P) and the extent of clustering behavior of modifiers (Na+) is determined through pair distribution function (PDF), total correlation function (TDF), coordination number (CN), Q x n distribution and oxygen speciation analysis. We show that Al-O-P and Si-O-Al linkage is preferred over other connections as compared to a random model and that Si-O-Si linkage is promoted by the P2O5 addition, which is related to structural heterogeneity and generates well-separated silicon-rich and aluminum-phosphorus-rich regions. Meanwhile, due to the relatively high propensity of Al to both Si and P, heterogeneity can be partly overcome with high Al content. A small amount of Si-O-P linkages have been detected at the interface of separated regions. Clustering of Na+ is also observed and intensified with the addition of P2O5. Based on the simulated structural information, a modified random network model for P2O5-bearing sodium aluminosilicate glass has been proposed, which could be useful to optimize the mobility of sodium ions and design novel functional glass compositions.

A sensitive immunoassay based on fluorescence resonance energy transfer from up-converting nanoparticles and graphene oxide for one-step detection of imidacloprid.

In this study, a fluorescence resonance energy transfer (FRET) immunoassay based on graphene oxide (GO) and up-converting nanoparticles (UCNPs) was established for rapid detection of imidacloprid, a commonly-used insecticide. Under 980 nm near-infrared light excitation, emission of UCNPs at 542 nm can be absorbed by the energy acceptor GO. The carboxyl-functionalized GO and UCNPs were coupled with competitive antigen and antibody against imidacloprid. After optimization, the FRET immunoassay showed a wide detection range of 0.08-50 ng/mL to imidacloprid, with cross-reaction toward other three neonicotinoids including imidaclothiz (74.4%), thiacloprid (36.9%) and clothianidin (31.9%). The average recoveries of spiked water, Chinese cabbage, cucumber, honey and tea samples were 76.8%-101.8%. The accuracy and reliability of the FRET immunoassay were verified by UPLC-MS/MS with a good correlation (R2 = 0.9816). In a summary, this study provides a sensitive and one-step method for monitoring imidacloprid residue in food and environmental samples within 1 h.

Temperature dependent molecular fluorescence of [Agm]n+ quantum clusters stabilized by phosphate glass networks.

Molecule like silver quantum clusters ([Agm]n+ QCs) exhibit an ultrasmall size confinement resulting in efficient broadband fluorescence. However, free [Agm]n+ QCs are also chemically active, so their stabilization is required for practical applications. We report in this work a phosphate oxyfluoride glass network enabled stabilization strategy of [Agm]n+ QCs. A series of silver-doped P2O5-ZnF2-xAg glasses were prepared by a conventional melt-and-quench method. The NMR and XPS results reveal that two types of [P(O,F)4] tetrahedrons (Q1, Q2) form chain structures and Zn(iv) connects [P(O,F)4] chains into a 3-dimension network in the glasses. The frameworks with limited void spaces were designed to restrict the polymerization degree, m, of [Agm]n+ QCs; the negatively charged tetrahedrons were designed to restrict the charge, n, of [Agm]n+ QCs. Through optical and mass spectroscopy studies, silver quantum clusters, [Ag2]2+ and [Ag4]2+, were identified to be charge compensated by [ZnO4] tetrahedrons and surrounded with [P(O,F)4] complex anions. The fluorescence thus gives high quantum efficiencies of 55.2% and 83.4%, for P2O5-ZnF2-xAg glass stabilized [Ag2]2+ and [Ag4]2+ QCs, respectively. This further reveals that the peak fixed fluorescence of [Ag2]2+ and [Ag4]2+ can be described by molecular fluorescence mechanisms. These are parity-allowed singlet-singlet transitions (S1 → S0), parity-forbidden triplet-singlet transitions (T1 → S0) and intersystem crossings between singlets (S1) and triplets (T1). The phonon coupled intersystem crossing between singlets (S1) and triplets (T1) determines the phosphate stabilized [Ag4]2+ QCs to exhibit a series of temperature dependent fluorescence behaviors. These include fluorescence intensity (at 50-200 K), intensity ratio (FIR) (at 50-200 K), peak shift (at 100-300 K) and lifetime (at 300-450 K) with maximum sensitivities of 1.27% K-1, 0.94% K-1, 0.29% K-1 and 0.41% K-1, respectively. Therefore, phosphate stabilized [Ag4]2+ QCs can be applied as temperature sensing probes, especially at low temperatures (10-300 K) and for color-based visualized temperature sensors.

A one-step mild acid route to fabricate high performance porous anti-reflective optical films from cationic polymeric nanolatex.

Porous silica anti-reflection (AR) films are of importance in solar cells' photon harvest. However, the usual utilized method to fabricate AR films is the two-step method since the formation of porous silica NPs (first step) and silica coating sol (second step) always require chemical systems at distinct pH values. To reduce the complexity of the process, we choose cationic emulsion as an approach to produce the porosity and propose a convenient one-step route to get high-performance antireflective films. A single layer SiO2 anti-reflective (AR) film with high optical transmittance up to 97.5% at 740 nm was fabricated from composite sol that was made from cationic emulsion nanolatex and tetraethylorthosilicate under acid catalysis condition. After calcination, the transmittance of AR coated glasses still held the transmittance of 96% at 550 nm. Composited with SiO2, Al2O3, or TiO2 sol binders, the transmittance of AR coated glasses could be recovered as high as 97.9% at 650 nm and the pencil hardness was further strengthened up to 6H. The composite sol can keep stable at least one month at ambient temperature without any visible precipitation. Therefore, the proposed method is promising for developing high-performance AR films effectively and economically.

Structure, Morphology, and Photoelectric Performances of Te-Sb2Se3 Thin Film Prepared via Magnetron Sputtering.

Antimony selenide (Sb2Se3) has been widely investigated as a promising absorber material for photovoltaic devices. However, low open-circuit voltage (Voc) limits the power conversion efficiency (PCE) of Sb2Se3-based cells, largely due to the low-charge carrier density. Herein, high-quality n-type (Tellurium) Te-doped Sb2Se3 thin films were successfully prepared using a homemade target via magnetron sputtering. The Te atoms were expected to be inserted in the spacing of (Sb4Se6)n ribbons based on increased lattice parameters in this study. Moreover, the thin film was found to possess a narrow and direct band gap of approximately 1.27 eV, appropriate for harvesting the solar energy. It was found that the photoelectric performance is related to not only the quality of films but also the preferred growth orientation. The Te-Sb2Se3 film annealed at 325 °C showed a maximum photocurrent density of 1.91 mA/cm2 with a light intensity of 10.5 mW/cm2 at a bias of 1.4 V. The fast response and recovery speed confirms the great potential of these films as excellent photodetectors.

Ultrastable Laurionite Spontaneously Encapsulates Reduced-dimensional Lead Halide Perovskites.

Reduced dimensional lead halide perovskites (RDPs) have attracted great research interest in diverse optical and optoelectronic fields. However, their poor stability is one of the most challenging obstacles prohibiting them from practical applications. Here, we reveal that ultrastable laurionite-type Pb(OH)Br can spontaneously encapsulate the RDPs in their formation solution without introducing any additional chemicals, forming RDP@Pb(OH)Br core-shell microparticles. Interestingly, the number of the perovskite layers within the RDPs can be conveniently and precisely controlled by varying the amount of CsBr introduced into the reaction solution. A single RDP@Pb(OH)Br core-shell microparticle composed of RDP nanocrystals with different numbers of perovskite layers can be also prepared, showing different colors under different light excitations. More interestingly, barcoded RDP@Pb(OH)Br microparticles with different parts emitting different lights can also be prepared. The morphology of the emitting microstructures can be conveniently manipulated. The RDP@Pb(OH)Br microparticles demonstrate outstanding environmental, chemical, thermal, and optical stability, as well as strong resistance to anion exchange processes. This study not only deepens our understanding of the reaction processes in the extensively used saturation recrystallization method but also points out that it is highly possible to dramatically improve the performance of the optoelectronic devices through manipulating the spontaneous formation process of Pb(OH)Br.

Visible-NIR Photodetectors Based on Low-Dimensional GeSe Micro-Crystals: Designed Morphology and Improved Photoresponsivity.

GeSe micro-sheets and micro-belts have been synthesized by a facile one-pot wet chemical method in 1-octadecene solvent and oleic acid solvent, respectively. The adsorption of more oleic acid molecules on the (002) plane promoted growth along [010] direction of the GeSe micro-belts and limited carrier transport in this direction, resulting in higher carrier concentration and mobility of the GeSe micro-belts. The performance of the photodetectors based on the single GeSe micro-sheet and the single GeSe micro-belt was investigated under illumination at 532 nm, 980 nm and 1319 nm. Both, photodetectors based on a single GeSe micro-sheet and a single GeSe micro-belt, exhibit a high photoresponse, short response/recovery times, and long-term durability. Moreover, the photodetector based on a single GeSe micro-belt displays a broadband response with a high responsivity (5562 A/W at 532 nm, 1546 A/W at 980 nm) and detectivity (3.01×1012 Jones at 532 nm, 8.38×1011 Jones at 980 nm). These excellent characteristics render single GeSe micro-belts very interesting for use as highly efficient photodetectors, especially in the NIR region.

Thermal Enhancement of Upconversion by Negative Lattice Expansion in Orthorhombic Yb2 W3 O12.

Thermal quenching of photoluminescence represents a significant obstacle to practical applications such as lighting, display, and photovoltaics. Herein, a novel strategy is established to enhance upconversion luminescence at elevated temperatures based on the use of negative thermal expansion host materials. Lanthanide-doped orthorhombic Yb2 W3 O12 crystals are synthesized and characterized by in situ X-ray diffraction and photoluminescence spectroscopy. The thermally induced contraction and distortion of the host lattice is demonstrated to enhance the collection of excitation energy by activator ions. When the temperature is increased from 303 to 573 K, a 29-fold enhancement of green upconversion luminescence in Er3+ activators is achieved. Moreover, the temperature dependence of the upconversion luminescence is reversible. The thermally enhanced upconversion is developed as a sensitive ratiometric thermometer by referring to a thermally quenched upconversion.

High performance optical temperature sensing via selectively partitioning Cr4+ in the residual SiO2-rich phase of glass-ceramics.

Quadrivalent Cr4+ theoretically exhibits great potential to achieve higher photo-luminescence (PL) lifetime based temperature sensitivity than the commonly utilized trivalent Cr3+, but the problem is how to stabilize the anomalous quadrivalent chemical state of Cr4+. Here we propose a type of glass-ceramic phase structure with a precipitated ZnAl2O4 crystalline sub-phase and a residual ZnO-SrO-SiO2 glassy sub-phase, where Cr4+ can be well stabilized in the residual glassy sub-phase. From PL spectra, Cr4+ or Cr3+ was found to be located at Td (tetrahedral crystal filed) or Oh (octahedral crystal filed) sites with a relatively high crystal field strength. The thermally coupled 1E(1D)/3T2(3F) states of Cr4+ or the 2E(2G)/4T2(4F) states of Cr3+ were revealed as competitive energy level pairs suitable for PL lifetime based temperature sensing. Quadrivalent Cr4+ had a particular PL lifetime ratio of 1E(1D)/3T2(3F) up to 103, which was much higher than that (101) of trivalent Cr3+:2E(2G)/4T2(4F). This supported Cr4+ to eventually achieve a higher temperature sensitivity (1.72% K-1) one order of magnitude higher than that of Cr3+ (0.83% K-1). This provides the possibility of utilizing Cr4+-doped glass to develop a type of temperature sensor with high precision and sensitivity.

Structural Origins of RF3/NaRF4 Nanocrystal Precipitation from Phase-Separated SiO2-Al2O3-RF3-NaF Glasses: A Molecular Dynamics Simulation Study.

Oxyfluoride glass-ceramics with RF3 or NaRF4 (R3+: rare earth elements) nanocrystals are considered as favorable hosts for luminescence applications. In this work, we utilized large-scale molecular dynamics (MD) simulations with effective partial charge potentials to study a series of oxyfluoride glasses that are of interest to the precipitation of RF3 or NaRF4 nanocrystals as previous experiment results suggested. The results show that phase separation exists in all glass compositions with fluoride-rich regions made up of R3+, Na+, and F- and oxide-rich regions consisting of aluminosilicate networks. These fluoride-enriched regions can serve as the precursor for RF3, cubic and hexagonal NaRF4, and NaF crystal precipitation. The results also confirm that the concentration of Na+ in the fluoride phase plays a key role in determining the crystal phases (RF3, NaRF4, or NaF) and crystal structure (cubic vs hexagonal NaRF4) to be precipitated. Consequently, this study shows that MD simulations with effective potentials can fill the gap in the structural understanding of oxyfluoride glass and provide insights into atomic scale information of the phase separation behavior that is useful in predicting the potential crystal types in oxyfluoride glass. When coupled with experimental validations, these simulations can expedite the exploration of novel luminescent oxyfluoride glass ceramics.

Phase separation strategy to facilely form fluorescent [Ag2]2+/[Agm]n+ quantum clusters in boro-alumino-silicate multiphase glasses.

By adjusting the content of ZnF2-SrF2/ZnO-SrO, a series of SiO2-Al2O3-B2O3-Na2O-ZnO/ZnF2-SrO/SrF2-Ag multiphase glasses was designed and prepared via a melt-quenching method. Under a phase separation strategy, negatively charged tetrahedrons ([BO4]-, [ZnO4]2-, and [AlO4]-) can be generated to stabilize different silver species (Ag+ ions; [Ag2]2+ pairs; [Agm]n+ quantum clusters ([Agm]n+ QCs)) in B2O3-rich and ZnO-Al2O3 rich sub-phases. The B2O3-rich sub-phase has a high solubility for Ag+ ions and [Agm]n+ QCs. The fluoride-rich phase shows a good ability to extract Na+ from the B2O3-rich sub-phase, significantly affects the solubility of Ag+ in the B2O3-rich sub-phase, and eventually determines the aggregation from Ag+ ions and Ag0 atom to [Agm]n+ QCs. The ZnO-Al2O3-rich or ZnO-SiO2-rich (i.e. SiO2-rich in GZnOSrO) phase has a relatively high solubility for [Ag2]2+ pairs. The Ag+/[Ag2]2+/[Agm]n+ QC fluorescent centers were identified by spectroscopic analysis, where the fluorescence bands are located in the ultraviolet, green-white and orange spectral regions, respectively. The fluorescent quantum yield (QY) of the [Agm]n+ QCs can be improved to 55.7%, and the combination of these three luminescent centers can achieve white light emission.

Yb3+-sensitized upconversion and downshifting luminescence in Nd3+ ions through energy migration.

A core-shell-shell nanostructure composed of NaGdF4:Yb/Tm@NaGdF4:Nd@NaYF4 is developed to realize Yb3+-sensitized upconversion and downshifting luminescence in Nd3+ ions. The unusual photon conversion property stems from a gadolinium sublattice mediated Yb3+→ Tm3+→ Gd3+→ Nd3+ energy transfer pathway. The energy transfer processes are investigated by varying the dopant concentration and distribution, in conjunction with time decay measurements.

Light-Emitting Diodes Based on Colloidal Silicon Quantum Dots with Octyl and Phenylpropyl Ligands.

Colloidal silicon quantum dots (Si QDs) hold ever-growing promise for the development of novel optoelectronic devices such as light-emitting diodes (LEDs). Although it has been proposed that ligands at the surface of colloidal Si QDs may significantly impact the performance of LEDs based on colloidal Si QDs, little systematic work has been carried out to compare the performance of LEDs that are fabricated using colloidal Si QDs with different ligands. Here, colloidal Si QDs with rather short octyl ligands (Octyl-Si QDs) and phenylpropyl ligands (PhPr-Si QDs) are employed for the fabrication of LEDs. It is found that the optical power density of PhPr-Si QD LEDs is larger than that of Octyl-Si QD LEDs. This is due to the fact that the surface of PhPr-Si QDs is more oxidized and less defective than that of Octyl-Si QDs. Moreover, the benzene rings of phenylpropyl ligands significantly enhance the electron transport of QD LEDs. It is interesting that the external quantum efficiency (EQE) of PhPr-Si QD LEDs is lower than that of Octyl-Si QD LEDs because the benzene rings of phenylpropyl ligands suppress the hole transport of QD LEDs. The unbalance between the electron and hole injection in PhPr-Si QD LEDs is more serious than that in Octyl-Si QD LEDs. The currently obtained highest optical power density of ∼0.64 mW/cm2 from PhPr-Si QD LEDs and highest EQE of ∼6.2% from Octyl-Si QD LEDs should encourage efforts to further advance the development of high-performance optoelectronic devices based on colloidal Si QDs.

Stabilization of divalent Eu2+ in fluorosilicate glass-ceramics via lattice site substitution.

Fluorosilicate glasses and glass-ceramics with MF2 (M = Ca, Sr, Ba), ZnF2 or LaF3 components were investigated to host divalent Eu2+ for photoluminescence (PL) application. X-ray diffraction phase identification and a series of spectroscopic analyses were performed to reveal the relationship between microstructure and the reduction of Eu3+ → Eu2+. The precursor glasses were believed being constituted by silicate-rich phases and fluoride-rich phases, due to the immiscibility of fluoride-and-silicate mixed glass system. After heat treatment, the fluoride-rich glass phases could transform into fluoride crystalline phase in the glass-ceramics. Europium tended to enrich in the fluoride-rich phases in the glasses or in the precipitated fluoride crystalline phases in the glass-ceramics. Small amounts of Eu3+ were reduced to Eu2+ in the glasses where the electronegativity had a crucial impact. In contrast, large amounts of Eu3+ were reduced to Eu2+ in the glass-ceramics containing MF2 nanocrystals, where the reduction was determined by lattice site substitution. Using ZnAl2O4 containing glass-ceramics as reference, it was evidenced that the similar and a little larger radii between sites and substitution ions are the prerequisite for Eu3+/M2+ substitution. And using LaF3 containing glass-ceramics as reference, it was certified that unbalanced charge at substitution sites induce the Eu3+ → Eu2+ reduction.