Phase evolution and photoluminescence in Er3+ doped glass ceramics containing lutetium oxyfluoride nanocrystals

Crystalline phase evolution through merely adjusting composition was achieved in silicate glass ceramics containing Lu_nO_n-1F_n+2 (n = 5–10) nanocrystals. Orthorhombic or cubic phase nanocrystals were precipitated in the aluminosilicate glass matrix after thermal treatment together with varying the Na₂O/NaF ratio. Oxyfluoride nanocrystals with quasi-spherical shape show homogenous and dense distribution in glass matrix by transmission electron microscopy measurement. Intense upconversion and mid-infrared emissions were realized in these glass ceramics compared to the precursor glass, and the emission spectral shapes, relative emission intensity and fluorescence decay curves of Er³⁺ in cubic LuOF embedded samples exhibit remarkable differences due to the crystal phase dependent effect in glass ceramics. These results indicate that the crystallization and luminescence properties of oxyfluoride glass ceramics could be modified through the alteration of glass composition, which could be used for the development of novel glass ceramics and design of luminescent properties.     

Optical properties of Er,Yb co-doped YAG transparent ceramics

The transparent polycrystalline erbium and ytterbium co-doped yttrium aluminum garnet (Er,Yb:YAG) ceramics with various Yb contents from 5% to 25% were prepared by the solid-state reaction and the vacuum-sintering technique. The in-line transmittances of the mirror-polished ceramics exceed 80% from the visible band to the infrared band. The samples are very compact with few pores. The average grain size of the Er,Yb:YAG ceramic is about 15 μm. The upconversion luminescence spectra, infrared luminescence spectra and luminescence decay curves of the ceramics were observed and discussed. For 1%Er doped YAG ceramic, the best ion ratio of Yb³⁺ and Er³⁺ is around 15:1.     

Effect of silica coating on the structural and luminescent properties of Sm3+/Yb3+ or Tm3+/Yb3+ co-doped TiO2 nanoparticles

The luminescent characteristics of spherical titanium dioxide (TiO₂) nanoparticles (NP's) doped with Sm³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ with and without a silica coating were analyzed. These nanoparticles were synthesized using the spray pyrolysis technique and coated with silica through a wet chemical process. The Sm³⁺/Tm³⁺ and Yb³⁺ doping induces a triphasic poly-crystalline structure of rutile and anatase TiO₂ and a Sm₂Ti₂O₇/Tm₂Ti₂O₇ cubic phase. A Williamson-Hall analysis was used to monitor the tensions of the NP's crystallites at the various doping concentrations and with addition of the silica shell. The luminescent spectra presented the characteristic emission peaks for the electronic energy levels transitions of the Sm³⁺/Tm³⁺ and Yb³⁺ ions. The Sm³⁺/Yb³⁺ co-doped NP's showed a maximum emission peak in the visible region at 612 nm, associated with ⁴G_5/2 → ⁶H_7/2 transitions of the Sm³⁺ ions. The IR emission peak at 973 nm (²F_5/2 → ²F_7/2) pertaining to Yb³⁺. For the combination of Tm³⁺/Yb³⁺, two emissions associated with Tm³⁺ ions were observed at 440 nm (¹D₂ → ³F₄) and 806 nm (³H₄ → ³H₆). The emission at 973 nm (²F_5/2 → ²F_7/2) is correlated to the Yb³⁺ ions. Silica coating of the NP's resulted in luminescence emission intensity increase of about 4 times.     

Photostimulated optical effects and some related features of CuO mixed Li2O–Nb2O5–ZrO2–SiO2 glass ceramics

We have synthesized Li₂O–Nb₂O₅–ZrO₂–SiO₂ glasses and subsequently crystallized them with different CuO contents (0–0.3 mol% in the steps of 0.05) as nucleating agents and characterized them by XRD, SEM and DSC. We have also studied IR, Raman, ESR, optical absorption photoluminescence and dielectric properties to explore the influence of copper valance states and their coordination with oxygen on structural and optoelectronic aspects of the samples. These studies have indicated that there is a possibility for the copper ions to exist in Cu⁺ and Cu³⁺ states (in addition to Cu²⁺ state) in these glass ceramics and participate in the glass network forming. Finally, we have undertaken photoinduced second harmonic generation studies (after the samples were dc field treated at elevated temperatures) with 10 ns Er:glass laser (of wavelength 1540 nm with power densities up to 1.5 GW/cm²) to examine the suitability of these materials for optically operated devices. The analysis of the results of non-linear optical studies has shown that 0.2 mol% of CuO is the optimal concentration for getting the highest values of second order susceptibility coefficients.     

Fabrication and properties of highly transparent Tm3Al5O12 (TmAG) ceramics

Highly transparent Tm₃Al₅O₁₂ (TmAG) ceramics were fabricated by solid-state reaction and vacuum sintering. Densification, microstructure evolution, mechanical, thermal, and optical properties of the TmAG ceramics were investigated. Fully dense TmAG ceramic with average grain size of 15 μm was obtained by sintering at 1780 °C for 20 h. The in-line transmittance was 80.5% at 2000 nm. The absorption coefficients at 682 nm and 785 nm were 8.03 cm⁻¹ and 8.33 cm⁻¹, respectively. The Vickers hardness, the Young modulus, the bending strength, and the fracture toughness values were 15.14 GPa, 343 GPa, 230 MPa, and 2.35 MPa m^1/2, respectively. The thermal conductivity at room temperature was 3.3 W/m K and the average linear thermal expansion coefficient from 20 °C to 1000 °C was 8.915 × 10⁻⁶ K.     

In vitro behavior of bioactive phosphate glass–ceramics from the system P2O5–Na2O–CaO containing titania

Soda lime phosphate bioglass–ceramics with incorporation of small additions of TiO₂ were prepared in the metaphosphate and pyrophosphate region, using an appropriate two-step heat treatment of controlled crystallization defined by differential thermal analysis results. Identification and quantification of crystalline phases precipitated from the soda lime phosphate glasses were performed using X-ray diffraction analysis. Calcium pyrophosphate (β-Ca₂P₂O₇), sodium metaphosphate (NaPO₃), calcium metaphosphate (β-Ca(PO₃)₂), sodium pyrophosphate (Na₄P₂O₇), sodium calcium phosphate (Na₄Ca(PO₃)₆) and sodium titanium phosphate (Na₅Ti(PO₄)₃) phases were detected in the prepared glass–ceramics. The degradation of the prepared glass–ceramics was carried out for different periods of time in simulated body fluid at 37 °C using granules in the range 0.300–0.600 mm. The released ions were estimated by atomic absorption spectroscopy and the surface textures were measured by scanning electron microscopy. Investigation of in vitro bioactivity of the prepared glass–ceramics was done by the measurement of the infrared reflection spectra for the samples after immersion in the simulated body fluid for different periods at 37 °C. The result showed that no apatite layer was formed on the surface of the samples and the dominant phase remained on the surface was β-Ca₂P₂O₇, which is known for its bioactivity.     

Color-tunable up-conversion emission from Yb3+/Er3+/Tm3+/Ho3+ codoped KY(MoO4)2 microcrystals based on energy transfer

Tunable up-conversion luminescent material KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) has been synthesized by a typical hydrothermal process. Under 980 nm laser diode (LD) excitation, the emission intensity and the corresponding luminescence colors of KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) have been investigated in detail. The energy transfer from the Yb³⁺ sensitizer to Ho³⁺, Er³⁺ and Tm³⁺ activators plays an important role in the development of color-tunable single- phased phosphors. The emission intensity keep balance through control of the Ho³⁺ co-doping concentrations, white light was experimentally shown at KY(MoO₄)₂: 20 mol% Yb³⁺, 0.8 mol% Er³⁺, 0.5 mol% Tm³⁺, 1.0 mol% Ho³⁺ phosphor with further calcination at 800 °C for 4 h under 980 nm laser excitation. The color tunability, high quality of white light and high intensity of the emitted signal make these up-conversion (UC) phosphors excellent candidates for applications in solid-state lighting.     

Nanocomposites based on chalcogenide glass semiconductor and metal phtalocyanine

A novel technique for the fabrication of chalcogenide nanocomposites based on chalcogenide glass (ChGs) and manganese phtalocyanine (MnPc) is presented. The structural and optical characterization of obtained composites in comparison to chalcogenide glass was carried out. Two-component nanocomposite films were obtained by simultaneous vacuum co-condensation of the ChGs components and organic dye on the substrate surface. The spatial arrangement of the two evaporators and substrates in a vacuum chamber allowed obtain samples with varied composite ratio. ChGs films optical band gap values were not sufficiently changed with growth rate and films thickness. It was shown that in case of dye concentration reduction for more than three orders specific absorption per dye molecule will be decreased by two orders. At greater concentrations solid solution of dye is clusterized, dye is distinctly aggregated and the absorbance is nearly the same as of the pure dye in the form of thin film. Therefore composite properties changes from cluster solution into molecular solution and thus dye molecule absorbance decrease. Relation of specific dye absorption on composite concentration was explained as electrons exchange with donor and acceptor subsystems and corresponding electron levels population. Sketch of electron density diagrams and corresponding bonds schema for composites are presented.     

Dielectric relaxation behavior and energy storage properties in Ba0.4Sr0.6Zr0.15Ti0.85O3 ceramics with glass additives

Ba_0.4Sr_0.6Zr_0.15Ti_0.85O₃ ceramics with SrO–B₂O₃–SiO₂ glass additives were prepared via the solid state reaction route. The effects of glass contents on the sintering behavior, dielectric properties, microstructures, and energy storage properties of BSZT ceramics were investigated. Dielectric breakdown strength of 22.4 kV/mm was achieved for BSZT ceramics with 20 wt% glass addition. Dielectric relaxation behavior was observed in dielectric loss versus temperature plots. In order to investigate the mechanism of dielectric breakdown performance, the relationship between dielectric breakdown strength and grain boundary barrier was studied by the measurements of breakdown strength and activation energy. A discharged energy density of 0.45 J/cm³ with an energy efficiency of 88.2% was achieved for BSZT ceramics with 5 wt% glass addition.     

Infiltration of Al2O3/Y2O3 mix into SiC ceramic preforms

Silicon carbide ceramics are very interesting materials to engineering applications because of their properties. These ceramics are produced by liquid phase sintering (LPS), where elevated temperature and time are necessary, and generally form volatile products that promote defects and damage their mechanical properties. In this work was studied the infiltration process to produce SiC ceramics, using shorter time and temperature than LPS, thereby reducing the undesirable chemical reactions. SiC powder was pressed at 300 MPa and pre-sintered at 1550 °C for 30 min. Unidirectional and spontaneous infiltration of this preform by Al₂O₃/Y₂O₃ liquid was done at 1850 °C for 5, 10, 30 and 60 min. The kinetics of infiltration was studied, and the infiltration equilibrium happened when the liquid infiltrated 12 mm into perform. The microstructures show grains of the SiC surrounded by infiltrated additives. The hardness and fracture toughness are similar to conventional SiC ceramics obtained by LPS.     

Enhanced upconverted luminescence and the optical thermometry behavior of Er3+-doped BaYbF5 transparent glass ceramics

Transparent SiO₂ - Al₂O₃ - Na₂O - CaO - BaF₂ - YbF₃ glass ceramics (GC) doped with Er³⁺ ions were successfully fabricated by a melt-quenching technique with subsequent heat treatment. The formation of BaYbF₅ nano-crystalline phase was confirmed by X-ray diffraction and transmission electron microscopy. Compared to the precursor glass (PG), the clearer Stark splitting and greatly enhanced up-conversion (UC) emission in GC indicate that Er³⁺ ions mainly enter into BaYbF₅ nanocrystals with low phonon energy after crystallization. The temperature dependent on purple UC emission ratio (which is due to the Er^{3+ 4}G_11/2→⁴I_15/2 and ²H_9/2→⁴I_15/2 transitions) and common green UC emission ratio with low-power excitation in BaYbF₅ GC have been studied respectively. In addition, the UC mechanisms in PG and GC are illustrated and analyzed. The outstanding properties of Er³⁺-doped BaYbF₅ transparent GC may present potential applications in all-solid-state UC lasers and optical fiber temperature sensors.     

Raman scattering, electronic structure and microwave dielectric properties of Ba([Mg1−xZnx]1/3Ta2/3)O3 ceramics

Effects of Zn substitution for Mg on the crystal structure, lattice vibrations and microwave dielectric properties of Ba(Mg_1/3,Ta_2/3)O₃ (BMT) ceramics were investigated. Raman scattering spectra for Ba([Mg_1−xZn_x]_1/3Ta_2/3)O₃ (BMZT) ceramics, with x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0, were measured at room temperature. The Raman result shows a dominance of 1:2 ordered structure at all Zn substitution contents. All Raman modes shift to lower frequencies with increasing Zn substitution. Higher Qf value correlates well with narrower width of the breathing Raman mode A_1g(4) and larger relative intensity of 1:2 long-range-ordered mode E_g(2) in BMZT solid solution. First-principle calculation was performed to investigate the electronic structure of 1:2 ordered BMT and Ba(Zn_1/3,Ta_2/3)O₃ (BZT). Covalent bond between Zn and O in BZT is much stronger than that between Mg and O in BMT due to the Zn 3d orbital. Zn substitution for Mg leads to longer and weaker Ta-O bonds, which may be one reason for the variation of Raman spectroscopy and microwave dielectric properties of BMZT system.     

Solid state reaction preparation and enhanced red luminescence of S-doped La2Mo2O9:Prphosphors

Red-light-emitting phosphors of La₂Mo₂O₉:Pr³⁺ and S-doped La₂Mo₂O₉:Pr³⁺ were prepared by high temperature solid state reaction. Under the excitation of 450 nm blue light, all samples produced a red emission peak at 650 nm corresponding to the characteristic transition of Pr³⁺ (³P₀→³F₂). The dependence of Pr³⁺ doping content (x) on the luminescent intensity was analyzed, and the optimal doping content of Pr³⁺ was x=0.07. After a small quantity of sulfur was introduced into the system, the luminescence intensity of phosphors was obviously enhanced. The reasons for the enhancement of luminescence are due to improved crystallization after S doping and the relatively large electronegativity difference between S and Mo. Additionally, the coincidence of the excitation wavelength with the emission of GaN chips may recommend this phosphor system as a potential candidate for use in white light-emitting diodes.     

Upconverting luminescence based dual-modal temperature sensing for Yb3+/Er3+/Tm3+: YF3 nanocrystals embedded glass ceramic

Yb³⁺/Er³⁺/Tm³⁺ doped transparent glass ceramic containing orthorhombic YF₃ nanoparticles was successfully synthesized by a melt-quenching method. After glass crystallization, tremendously enhanced (about 5000 times) upconversion luminescence, obvious Start-splitting of emission bands as well as long upconversion lifetimes of Er³⁺/Tm³⁺ confirmed the incorporation of lanthanide activators into precipitated YF₃ crystalline environment with low phonon energy. Furthermore, temperature-dependent upconversion luminescence behaviors of glass ceramic were systematically investigated to explore its possible application as optical thermometric medium. Impressively, both fluorescence intensity ratio of Er³⁺: ²H_11/2 → ⁴I_15/2 transition to Er³⁺: ⁴S_3/2 → ⁴I_15/2 one and fluorescence intensity ratio of Tm³⁺: ³F_2,3 → ³H₆ transition to the combined Tm³⁺: ¹G₄ → ³F₄/Er³⁺: ⁴F_9/2 → ⁴I_15/2 ones were demonstrated to be applicable as temperature probes, enabling dual-modal temperature sensing. Finally, the thermal effect induced by the irradiation of 980 nm laser was found to be negligible in the glass ceramic sample, being beneficial to gain intense and precise probing signal and detect temperature accurately.     

Gd3+ doping induced enhanced upconversion luminescence in Er3+/Yb3+ co-doped transparent oxyfluoride glass ceramics containing NaYF4 nanocrystals

In this article, transparent oxyfluoride glass ceramics containing $\mathrm{\beta }$-NaYF₄ nanocrystals were successfully prepared via Gd³⁺ doping. Compared to conventional non-doped glasses, the thermal treatment temperature required for the precipitation of $\mathrm{\beta }$-NaYF₄ nanocrystals can be lowered with the doping of Gd³⁺. Furthermore, under the same thermal treatment condition, more $\mathrm{\beta }$-NaYF₄ nanocrystals were precipitated in Gd³⁺ doped ones, which greatly improves the luminescence efficiency of rare earth doped glass ceramics. Possible mechanism for the Gd³⁺ doping induced enhanced upconversion luminescence phenomenon was proposed, based on thorough structural and optical characterizations. The results revealed that the doping of Gd³⁺ ions could decrease the crystallization activation energy and promote the formation of Y-F-Na bonding, which helps the precipitation of $\mathrm{\beta }$-NaYF₄ nanocrystals. Consequently, a large enhancement in upconversion luminescence was achieved. Moreover, the strategy can be successfully applied to the development of other glass ceramic systems for various optoelectronic applications.     

Large-scale synthesis of WO3 nanoplates by a microwave-hydrothermal method

Tungsten oxide (WO₃) nanoplates were synthesized by a 270 W microwave-hydrothermal reaction of Na₂WO₄·2H₂O and citric acid (C₆H₈O₇·H₂O) in deionized water. X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) were used to reveal the synthesis of WO₃ complete rectangular nanoplates in the solution of 0.2 g citric acid for 180 min, with O-W-O FTIR stretching modes at 819 and 741 cm⁻¹, and two prominent O-W-O Raman stretching modes at 804 and 713 cm⁻¹. The 2.71 eV indirect energy gap, and 430-460 nm blue emission wavelength range of WO₃ complete rectangular nanoplates were determined using UV-visible and photoluminescence (PL) spectrometers. The formation mechanism was also proposed according to the experimental results.     

Preparation and characterizations of highly transparent UV-curable ZnO-acrylic nanocomposites

A sol–gel chemical route was adopted to prepare the zinc oxide (ZnO) nanoparticles as small as 4 nm. UV-curable ZnO-acrylic nanocomposites were then prepared by employing 3-(trimethoxysilyl)propyl methacrylate (TPMA) as the surface modification agent of ZnO particles. UV–vis analysis revealed a high optical transparency (>95%) in visible light region for nanocomposite thin films with ZnO contents up to 20 wt.%. The addition of ZnO nanoparticles also enhanced the dielectric constants of nanocomposites and the dielectric constants greater than 4 in frequencies ranging from 1 to 600 MHz was obtained in the samples containing 10 wt.% of ZnO nanoparticles. A comparison of experimental results and theoretical calculation indicated that the interfacial polarizations in between ZnO nanoparticles and polymer matrix may play an important role in the enhancement of dielectric properties of nanocomposites.     

Optical and ferromagnetic properties of hydrothermally synthesized CeO2/CuO nanocomposites

Nanostructured CeO₂/CuO composites are synthesized using a facile hydrothermal reaction. Results signify that Cu ions prefer to enter into CeO₂ lattice forming solid solution at low concentration, and would be transformed into CuO phase at moderate concentration. Moreover, the addition of CuO species into CeO₂ promotes the reduction of Ce⁴⁺ and the creation of oxygen vacancy (V_O) defects. Raman analyses confirm V_O concentration initially increases and then decreases with the increasing CuO phase and the sample Ce1Cu2 exhibits the highest defect concentration. The room temperature ferromagnetic behavior is observed firstly in CeO₂/CuO nonmagnetic system and the maximal saturation magnetization appears in Ce1Cu2. The emergent ferromagnetism appears to be relevant to the extensive V_O defects, which can be interpreted by the indirect double-exchange model. The synthetic interaction between CeO₂ and CuO results in the redshift of the bandgap in prepared CeO₂/CuO nanocomposites.     

Largely enhanced mechanoluminescence properties in Pr3+/Gd3+ co-doped LiNbO3 phosphors

Pr³⁺/Gd³⁺ co-doped LiNbO₃ phosphors were prepared by a traditional solid-state reaction method and their structure, photoluminescence, mechanoluminescence and thermoluminescence were investigated. The results showed that the LiNbO₃ phase with a rhombohedral structure and an R3c space group was successfully prepared. Mechanoluminescence intensity in nonstoichiometric LiNbO₃:Pr³⁺ was largely increased by introducing Gd³⁺ ions. The optimal co-doped concentration of Gd³⁺ was 1?mol% and the enhanced ML intensity of LiNbO₃:0.01Pr³⁺, 0.01Gd³⁺ was about 177% times compared with that of LiNbO₃:0.01Pr³⁺. The effect of Gd³⁺ co-dopants on trap levels were explored through thermoluminescence curves. The enhancement of mechanoluminescence intensity was suggested to be ascribed to the regulated trap quantities caused by co-doped Gd³⁺ ions. Appropriate co-dopants are proved to be effective sensitizers for mechanoluminescence materials.     

Fabrication and piezoelectric properties of BaTiO3/BaTiO3-Bi(Mg1/2Ti1/2)O3-BiFeO3 composites

We fabricated xBaTiO₃ (BT)/(1-x)[BaTiO₃-Bi(Mg_1/2Ti_1/2)O₃-BiFeO₃] (BT-BMT-BF)?+?0.1?wt%MnCO₃ composites by spark plasma sintering and investigated the effect of BT content x, BT powder size, and BT-BMT-BF composition on piezoelectric properties. For xBT/(1-x)(0.3BT-0.1BMT-0.6BF) +?0.1?wt%MnCO₃ (x?=?0–0.75) composites with a 0.5-µm BT powder, the dielectric constant was increased with x, and the relative density was decreased at x?=?0.67 and 0.75, creating optimum BT content of x?=?0.50 with a piezoelectric constant d₃₃ of 107?pC/N. When a larger 1.5-µm BT powder was utilized for the composite with x?=?0.50, the d₃₃ value increased to 150?pC/N due to the grain size effect of the BT grains. To compensate for a compositional change from the optimum 0.3BT-0.1BMT-0.6BF due to partial diffusion between the BT and 0.3BT-0.1BMT-0.6BF grains, a 0.5BT/0.5(0.275BT-0.1BMT-0.625BF)?+?0.1?wt%MnCO₃ composite with the 1.5-µm BT powder was fabricated. We obtained an increased d₃₃ value of 166?pC/N. These results provided a useful composite design to enhance the piezoelectric properties.