Doping effects of Mn<Superscript>2+</Superscript> on the dielectric properties of glass-doped BaTiO<Subscript>3</Subscript>-based X8R materials

In this paper, Mn²⁺ and calcium borosilicate glass (CBS) were used as effective dopants to prepare environmentally friendly dielectric materials satisfying EIA X8R specification. The effects of various Mn²⁺ concentrations on the dielectric properties of BaTiO₃ (BT) ceramics were investigated when CBS amount was fixed. The dielectric measurements showed that the permittivity was decreased continuously with increasing Mn²⁺ concentrations, resulted from the existence of paraelectric regions caused by Mn²⁺ doping. The dielectric loss was decreased at the beginning and then increased with increasing Mn²⁺ concentrations, whereas the resistivity showed an opposite movement. The SEM images and X-ray diffraction curves corresponding to BT ceramics doped with different Mn²⁺ amounts proved that Mn²⁺ can promote the crystallization of CBS glass to form the secondary phase Ca₄Mn₄Si₈O₂₄, which determines the intensity of the high temperature peak (at about 125 °C) of the variation rate curve of capacitance. Moreover, the modification effects of Mn²⁺ on the dielectric properties of BT have been investigated. It is revealed that a proper usage of Mn²⁺ can improve the dielectric properties significantly, and Mn²⁺ and CBS co-doped BT ceramics are promising to develop X8R MLCs.     

Persistent luminescence of Zn<Subscript>2</Subscript>GeO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>/Pr<Superscript>3+</Superscript> phosphors

Zn₂GeO₄, Zn₂GeO₄:Mn²⁺, Zn₂GeO₄:Pr³⁺ and Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors were fabricated by a solid state reaction. The phase and luminescent properties of the fabricated phosphors were investigated. The XRD patterns show that all of the fabricated phosphors have an orthorhombic structure. The fabricated Zn₂GeO₄ shows an emission band in the range of 350–550 nm. The fabricated Zn₂GeO₄:Mn²⁺ and Zn₂GeO₄:Pr³⁺ phosphors show emission bands corresponding to Mn²⁺ and Pr³⁺ ions, respectively. The fabricated Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor shows the emission band results from Mn²⁺ and the codoped Pr³⁺ enhances the emission intensity of Mn²⁺. Moreover, Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor exhibits longer decay time than that of Zn₂GeO₄:Mn²⁺. The higher intensity and longer lifetime of Mn²⁺ emission are induced by the energy transfer from Pr³⁺ of various vacancies to Mn²⁺ in Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors.     

Influence of Mn<Superscript>2+</Superscript> on the up-conversion emission performance of Mn<Superscript>2+</Superscript>, Yb<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>: ZnWO<Subscript>4</Subscript> green phosphors

The Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors are synthesized successfully through the high temperature solid state reaction method. The micro-structure and morphology have been investigated by means of XRD and EDS. The doped concentrations of Mn²⁺, Yb³⁺, Er³⁺ are measured by ICP. The absorption spectra and emission spectra with different doped concentrations of Mn²⁺ are presented to reveal the influence of Mn²⁺ on the green up-conversion performance. Excited with 970 nm LED, the up-conversion emission peak at 547 nm is obtained and the CIE spectra as well as the green light photo are also presented. The results indicate that the Mn²⁺ ions play the role of the luminescence adjustment in the up-conversion process, which can improve the up-conversion green emission intensity effectively. The luminescence adjustment mechanism of Mn²⁺ ions in Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors has been discussed. The crystal parameters of Dq, B and C are calculated to evaluate the energy level split effect.     

Effect of sintering temperature on the emission-spectrum-shape-evolution of Sr<Subscript>2</Subscript>SiO<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript> phosphor

Color rendering index and color temperature are the key factors for the LEDs application. The two points are closely related to the emission spectrum shape of phosphors. As the key factors for the LEDs application, both the above aspects are closely dependent on the emission spectrum shape of phosphors. In this study, the emission spectrum shape has been adjusted via a home designed route. A combination of structural, morphological, and optical characterization techniques has been used to study the shape evolution mechanism. The structural results show that the Sr₂SiO₄ phase has not been changed with the sintering temperature increasing, but the emission spectrum shape has changed dramatically, meanwhile, the colorimetric coordinate moves from blue-green to green region. Gaussian fitting method has been used to treat the emission spectrum, and the as-obtained results indicate the emission spectrum contains two single bands, which come from the 4f⁷(⁷S_7/2)–4f⁶(⁷F_J)5d¹ transition of Eu²⁺ on the different Sr sites in the Sr₂SiO₄ crystal. The intensity of the two single bands is driven by sintering temperature, because of the difference between the energy barrier of the Eu²⁺ occupying the different Sr sites in the matrix crystal. Moreover, the mechanism of the above phenomenon has also been studied by means of first principles method, and the obtained results agree well with the former deduction.     

Preparation of BaTiO<Subscript>3</Subscript>-based ceramics by nanocomposite doping process

BaTiO₃-based ultrafine nonreducible dielectrics for multilayer ceramic capacitors were prepared by a newly developed nanocomposite doping process. According to TG-DTA, XRD and TEM analysis, the nanocomposite dopants via sol–gel method were uniform and well dispersive. The micromechanism was investigated based on comparing conventional process with nano-doping process. It indicated that due to the special nano-effect, doping effect of additives became more effective and the microstructure and dielectric properties of ceramics were improved. The results showed that high performance dielectrics satisfying X8R specification were achieved, with high dielectric constant of 2,900, low dielectric loss of 0.6% and large insulation resistivity of 10¹² Ω cm.     

Effect of coactivation with Dy<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions on the efficiency of energy storage in Lu<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Ce<Superscript>3+</Superscript> crystals

Cerium-activated lutetium oxyorthosilicate Lu₂SiO₅:Ce³⁺ (LSO:Ce) and coactivated LSO:Ce,Dy and LSO:Ce,Yb crystals have been synthesized by the sol-gel technique. It is shown that the introduction of coactivator (Yb and Dy) ions influences the energy storage in LSO:Ce, thus making it possible to control the afterglow and thermoluminescence in these crystals. The observed effect is related to the electron properties of coactivator ions (donor against acceptor), which determine the recharge of electron traps in LSO crystals.     

Morphology and luminescent properties of Al<Superscript>3+</Superscript>/Mg<Superscript>2+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Al³⁺/Mg²⁺ doped Y₂O₃:Eu phosphor was synthesized by the glycine-nitrate solution combustion method. In contrast to Y₂O₃:Eu which showed an irregular shape of agglomerated particles (the mean particle size >10 μm), the morphology of Al³⁺/Mg²⁺ doped Y₂O₃:Eu crystals was quite regular. Al³⁺/Mg²⁺ substituting Y³⁺ in Y₂O₃:Eu resulted in an obvious decrease of the particle size. Meanwhile, higher the Al³⁺/Mg²⁺ concentration, smaller the particle size. In particular, the introduction of Al³⁺ ion into Y₂O₃ lattice induced a remarkable increase of PL and CL intensity. While, for Mg²⁺ doped Y₂O₃:Eu samples, their PL and CL intensities decreased. The reason that causes the variation of PL and CL properties for Al³⁺ and Mg²⁺ doped Y₂O₃:Eu crystals was concluded to be related to sites of Al³⁺ and Mg²⁺ ions inclined to take and the difference of ion charge.     

Microwave-hydrothermal synthesis of nano-sized Sn<Superscript>2+</Superscript>-doped BaTiO<Subscript>3</Subscript> powders and dielectric properties of corresponding ceramics obtained by spark plasma sintering method

Ternary oxides containing Sn²⁺ are rare and difficult to prepare using solid state reaction due to disproportionation of Sn²⁺ at high temperature. In this paper, nanoparticles of barium titanate doped with different amounts of Sn²⁺ consisting of single phase perovskite structure were successfully synthesized for the first time by using a microwave-assisted solvothermal reaction. The particle sizes were about 20–40 nm in diameter and increased with increasing the amount of doped tin. Solidified ceramic bodies were obtained using a spark plasma sintering method under argon atmosphere avoiding the disproportionation and oxidation of Sn²⁺ in the air. The grain size and dielectric constant of the sintered body decreased with increasing the amount of doped tin.     

Large enhancement of upconversion luminescence in Er<Superscript>3+</Superscript>/In<Superscript>3+</Superscript>:Ba<Subscript>0.85</Subscript>Ca<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript> lead-free piezoelectric ceramics

A series of In³⁺-doped Ba_0.85Ca_0.15TiO₃:0.75%Er³⁺/xIn³⁺ (BCT:Er/xIn) lead-free piezoelectric ceramics with excellent upconversion luminescence were synthesized by the solid state reaction method. The effects of In³⁺ content on the crystal structure, ferroelectric, dielectric, piezoelectric, and upconversion luminescence properties were systematically studied. Under 980 nm excitation, a giant enhancement of the green emission (550 nm) by 10 times is achieved upon 2.5% mol In³⁺ doping, which is rarely observed in rare-earth ions-doped perovskite ferroelectric materials. The ultraviolet-visible-near infrared absorption measurements show that the In³⁺ doping may improve the dissolution of Er³⁺ ions and modify the isolate-/clustered-Er³⁺ ratio for x?≤?2.5%, resulting in the enhancement of the absorption cross-section, thereby contributing to the enhancement of green luminescence. Unfortunately, the In³⁺ doping suppresses the ferroelectric and piezoelectric properties of the BCT:Er/xIn ceramics. This problem can be resolved by adding a small amount (1 mol%) of Yb³⁺ to the BCT:Er/xIn ceramics to restore their good ferroelectric and piezoelectric properties. Such In³⁺ and rare-earth ions co-doped ceramics with greatly enhanced upconversion luminescence and good ferroelectricity and piezoelectricity may have potential applications in electro-optical devices.     

PTCR effect in BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript>-doped BaTiO<Subscript>3</Subscript> ceramics

The influences of BaBi₂Nb₂O₉ content on the electrical property and the microstructure of BaTiO₃-based materials have been studied. With an increase in BaBi₂Nb₂O₉ content the grain size decreases. All the prepared BaBi₂Nb₂O₉ doping BaTiO₃-based thermistors show typical PTC effect. As the amount of BaBi₂Nb₂O₉ added in BaTiO₃-based ceramics increases, resistivity appears to exhibit a minimum value. At high BaBi₂Nb₂O₉ content (≥0.0875), the resistivity increased again with increasing BaBi₂Nb₂O₉ content. At a given content of BaBi₂Nb₂O₉, the influence of sintering temperature on the electrical properties of samples has been investigated. A minimum of room temperature resistivity is obtained at the sintering temperature equal to 1,290 °C at a given content of BaBi₂Nb₂O₉.     

Influence of Mg<Superscript>2+</Superscript>/Ga<Superscript>3+</Superscript> doping on luminescence of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> phosphors

Mg²⁺/Ga³⁺ doped Y₃Al₅O₁₂:Ce³⁺ phosphors were synthesized through a solid state reaction. The phase and luminescent of the synthesized phosphors were investigated. For Ga³⁺ codoped Y_2.96Ce_0.04Al_(5?x)Ga_xO₁₂ phosphors, the emission intensity increases with the increase of Ga³⁺ concentration up to Y_2.96Ce_0.04Al_4.80Ga_0.20O₁₂ and then decreases with a further increase of Ga³⁺ concentration, but the emission peak shifts to shorter wavelength continuously in the Ga³⁺ doping concentration range of 0.05–0.25. For Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors, the emission intensity decreases and the emission peak shifts to longer wavelength continuously in the Mg²⁺ doping concentration range of 0.02–0.12. The emission spectra of Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors demonstrate that the codoped Mg²⁺/Ga³⁺ ions not only induce the enhancement of Y_2.96Ce_0.04Al₅O₁₂ emission intensity but also lead to the red shift of Y_2.96Ce_0.04Al₅O₁₂ emission peak. The decay lifetimes decrease in Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al₅O₁₂ phosphors due to defects formed by substitutions of Y³⁺ by Mg²⁺/Ga³⁺.     

Effect of BaTiO<Subscript>3</Subscript> heat treatment on the microstructure and dielectric properties of BaTiO<Subscript>3</Subscript>-based ceramics

We have studied the effect of heat treatment of the starting BaTiO₃ powder on the dielectric properties and microstructure of X7R-type BaTiO₃-based ceramics. The results demonstrate that annealing of BaTiO₃ stabilizes the degree of tetragonality in the crystal lattice of the ceramics. Microstructural analysis shows that the annealing temperature has no effect on the average grain size of the ceramics. Increasing the BaTiO₃ annealing temperature increases the dielectric permittivity of the core phase and reduces the temperature coefficient of capacitance (TCC). We obtained an X7R-type BaTiO₃-based ceramic material (BaTiO₃ annealing temperature, 1150°C; firing temperature, 1160°C) with the following properties: ɛ_25°C = 2230, TCC = ±12% (−55 to 125°C), and tanδ_25°C = 0.013.     

Phase conversion and spectral properties of long lasting phosphor Zn<Subscript>3</Subscript> (PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Mn<Superscript>2+</Superscript>, Ga<Superscript>3+</Superscript>

A red long lasting phosphor Zn₃(PO₄)₂:Mn²⁺,Ga³⁺ (ZPMG) was prepared by ceramic method, and phase conversion and spectral properties were investigated. Results indicated that the phase conversion from α-Zn₃(PO₄)₂, β-Zn₃(PO₄)₂ toγ-Zn₃(PO₄)₂ occurs with different manganese concentration incorporated and sinter process. The structural change induced by the phase transformation results in a remarkable difference in the spectral properties. The possible luminescence mechanism for this red LLP with different forms has been illustrated.     

Luminescent properties of Pb<Superscript>2+</Superscript>- and Mn<Superscript>2+</Superscript>-activated CdI<Subscript>2</Subscript> crystals

The luminescent properties of CdI₂, CdI₂:Pb²⁺, CdI₂:Mn²⁺, and CdI₂:Pb²⁺,Mn²⁺) crystals have been studied at temperatures from 85 to 295 K under optical and x-ray excitation. Analysis of new and earlier spectroscopic data suggests that the 560-nm luminescence of CdI₂:Pb²⁺ and CdI₂:(Pb²⁺,Mn²⁺) crystals under excitation on the long-wavelength component of the A absorption band of Pb²⁺ centers is due to Pb²⁺-bound anion excitons. The 640-to 660-nm emission of these crystals is attributable to α centers. The manganese luminescence in the codoped material originates from both intracenter Mn²⁺ excitations and a sensitized process due to energy transfer from the host and Pb²⁺-related centers. The mechanisms of recombination and energy transfer processes in cadmium iodide crystals codoped with Pb²⁺ and Mn²⁺ are discussed.     

SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> fibers from titanium-modified polycarbosilane

We developed a process for preparing SiO₂/TiO₂ fibers by means of precursor transformation method. After mixing PCS and titanium alkoxide, continuous SiO₂/TiO₂ fibers were fabricated by the thermal decomposition of titanium-modified PCS (PTC) precursor. The tensile strength and diameter of SiO₂/TiO₂ fibers are 2.0 GPa, 13 μm, respectively. Based on X-ray diffraction (XRD), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HRTEM) measurements, the microstructure of the SiO₂/TiO₂ fibers is described as anatase–TiO₂ nanocrystallites with the mean size of ~10 nm embedded in an amorphous silica continuous phase.     

Mechanochemical synthesis of BaTiO<Subscript>3</Subscript> using different forms of TiO<Subscript>2</Subscript>

Reactions between barium oxide and different forms of titanium dioxide during milling in air and subsequent heat treatment have been studied by X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. The results indicate that, when the low-temperature forms of TiO₂ are used, milling produces weakly aggregated barium titanate powders with a large specific surface area.     

Structure and luminescent properties of Cs<Subscript>2</Subscript>Sr(VO<Subscript>3</Subscript>)<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>

We have developed a procedure for thermally stimulated synthesis of a cesium strontium metavanadate, Cs₂Sr(VO₃)₄:Mn²⁺ (0.01, 0.50, 1.00, 5.00 at % Mn²⁺), using MnO-containing starting mixtures. The EPR spectrum of the material containing 0.01 at % Mn²⁺ shows a hyperfine structure due to the incorporation of a small amount of manganese into the diamagnetic double metavanadate host. The luminescent and optical properties of Cs₂Sr(VO₃)₄:Mn²⁺ depend on manganese content. In contrast to higher doping levels, doping with 0.01 at % Mn²⁺ increases the integrated emission intensity of the vanadate by 10% and improves its chromaticity characteristics (approaching them to those of white light). We assume that this is due to the reduction in the density of vacancy-type growth defects, such as oxygen vacancies.     

Fabrication and properties of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> composites

Composites in the form of precipitated powders, hybrid xerogels, and SiO₂ core/TiO₂ shell particles have been produced via hydrolysis of precursors (alkoxides and inorganic derivatives of titanium and silicon) and have been characterized by differential thermal analysis, X-ray diffraction, adsorption measurements, and macroelectrophoresis. The results demonstrate that heat treatment of the composites leads to crystallization of the titanium-containing component and, accordingly, reduces their specific surface area. Hydrothermal treatment enables the fabrication of materials in which TiO₂ nanocrystals are evenly distributed over an amorphous SiO₂ matrix.     

X-ray diffraction,optical absorption and emission studies on Er<Superscript>3+</Superscript>- and Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>NbO<Subscript>4</Subscript> powder

Er³⁺(/Yb³⁺)-doped Li₃NbO₄ powder were prepared by thermally sintering mixtures of Er₂O₃ (0.5, 1.0 mol%), Yb₂O₃ (0, 0.5, 1.0 mol%), Li₂CO₃ (48–49 mol%) and Nb₂O₅ (50 mol%) at 1125, 1150 and 1450 °C over the durations of 8–22 h. The crystalline phases contained in these samples were determined by using X-ray diffraction and discussed in comparison with a vapor-transport-equilibration-treated (VTE-treated) Er(2.0 mol%):LiNbO₃ single crystal and ErNbO₄ powder previously reported. The results show that the X-ray patterns of the rare-earth-doped samples reveal little difference each other, but large differences with those of the VTE crystal and ErNbO₄ powder. The doped rare-earth ions Er³⁺ (and Yb³⁺) present in the powder as the ErNbO₄ (and YbNbO₄) phase(s). The possibility that the highly Er-doped LiNbO₃ crystal contains Li₃NbO₄ precipitates is small. Optical absorption and emission studies show that the only Er-doped Li₃NbO₄ powder shows similar absorption and emission characteristics with the pure ErNbO₄. The codopant Yb³⁺ ion enhances the 980-nm-upconversion emissions of Er³⁺ ions, results in remarkable spectral alterations at 0.98 μm region, and causes the alterations of relative absorbance and relative emission intensity of individual peaks or bands at 1.5 μm region. On the other hand, the Yb-codoping hardly affects the Er³⁺ energy structure and the lifetime of Er³⁺ ion at 1.5 μm. The measured lifetimes at 1.5 μm of Er³⁺ ions in the singly Er³⁺- and doubly Er³⁺/Yb³⁺-doped mixtures have a nearly same value of ∼ 1.5 ms. For the pure ErNbO₄ powder, the lifetime is prolonged to ∼2 ms perhaps due to radiation trapping effect.     

A comparative study of different solvothermal methods for the synthesis of Sn<Superscript>2+</Superscript>-doped BaTiO<Subscript>3</Subscript> powders and their dielectric properties

Ternary oxides containing Sn²⁺ are rare and difficult to prepare by the conventional solid state reactions due to the disproportionation of Sn²⁺ to Sn⁴⁺ and Sn at high temperatures. In this article, Sn²⁺-doped barium titanate, Ba_1−x Sn _x TiO₃ (x = 0.00, 0.02, 0.05, and 0.10) nanopowders were successfully synthesized at a moderate temperature by a microwave-assisted solvothermal reaction (MSR) and a solvothermal reaction with rolling (SRR). The powders obtained using the MSR and SRR consisted of nanoparticles of 20–50 nm and 100–120 nm in diameter, respectively. The dielectric constant of the sample increased by doping with a small amount of Sn²⁺ (x ≤ 0.05), but decreased by doping in excess amounts of it.