Effects of SiC on phase transformation and microstructure of spark plasma sintered α/β-SiAlON composite ceramics

α/β-SiAlON/SiC composite ceramic tool materials were prepared via spark plasma sintering. The effects of content and size of SiC particles and sintering temperature on phase composition, mechanical properties, and microstructure were investigated. The results indicated that SiC restrained the transformation of β-SiAlON to α-SiAlON, but higher SiC content (≥10 wt.%) resulted in a higher Vickers hardness of the composite. The large size of SiC particles raised the densification temperature of α/β-SiAlON composites, and small SiC particles benefited to improve microstructure. There were more equiaxed α-SiAlON grains and β-SiAlON with a larger aspect ratio (${\overline{\alpha }}_{95}$ = 5.1) in the α/β-SiAlON composite containing 100 nm SiC. The sample containing 10 wt.% 100 nm SiC particles sintered at 1700°C had the optimal properties with a Vickers hardness and fracture toughness of 18.5 ± .2 GPa, 6.4 ± .2 MPa m^1/2, respectively.     

Effects of Nb/TiC/TaC/VC and Co addition on the microstructure and properties of WC-based cemented carbides

A series of WC-based cemented carbides with Nb/TiC/TaC/VC and Co was prepared through spark plasma sintering (SPS) at a low sintering temperature of 1300°C, and their microstructures and mechanical properties were investigated. The nonstoichiometric multicomponent carbide Nb/TiC/TaC/VC with a rock-salt structure ($Fm\overline{3}m$) has a high atomic solution capacity. In the sintering process, partial WC and Co may dissolve in Nb/TiC/TaC/VC. With a high concentration of carbon vacancies, Nb/TiC/TaC/VC plays a beneficial role as a mass transfer intermediary. Good mass transfer facilitates the formation of a more accommodating and stable bonding between WC, Nb/TiC/TaC/VC, and Co, thereby preserving the hardness of the sintered bulks and preventing the initiation and propagation of cracks. When 6 wt.% Nb/TiC/TaC/VC and 4 wt.% Co are added to WC, the sintered bulk with fine grains exhibits superior hardness (23.27 ± .63 GPa) and toughness (10.45 ± .56 MPa·m^1/2).     

Crystal structure and magneto-dielectric properties of Co-Zr co-substituted Co2Z hexaferrites

A series of Ba_1.5Sr_1.5Co_2+xZr_xFe_24-2xO₄₁ hexaferrites (x = 0.00, 0.01, 0.03, 0.05, 0.07, and 0.09) were successfully prepared by the conventional solid-state reaction method. It was found that as the Co²⁺ and Zr⁴⁺ ions entered the hexaferrite structure, the lattice parameters increased, whereas the relative density increased when x = 0.00-0.03 and then decreased. A suitable amount of substitution increased the DC resistivity, reduced the magnetic and dielectric losses, and made the ${\mu }^{\prime }$ and ${\epsilon }^{\prime }$ closer to each other. At x = 0.03, the relative density and DC resistivity of the samples reached their maxim. Besides, both the magnetic and dielectric losses were lowest within the frequency range of 10 MHz-1 GHz. Meanwhile, the hexaferrite was impedance matched to free space, and the miniaturization factor was about 15. Therefore, this low-loss ferrite with almost equal permeability and permittivity could be meaningful for antenna miniaturization and high-frequency applications.     

Microstructures and physical properties of sol–gel derived Ba2FeMnO6 double perovskite

We report microstructures and physical (dielectric, magnetic, and optical) properties of sol–gel derived Ba₂FeMnO₆ (BFMO) double perovskite powders. The BFMO powders belong to hexagonal crystal structure with P-6m2 space group. SEM images reveal the powders are nearly homogeneous distribution with spherical morphology and average particle size of 300 nm. Energy-dispersive spectra gave out the molar ratio of the Ba:Fe:Mn elements equal to 2.16:1.00:1.00. FTIR spectrum verified the [FeO₆] and [MnO₆] octahedra present in the powders. X-ray photoelectron spectroscopy spectra identified the chemical valence states of the constituent elements. The BFMO ceramics displayed a strong frequency dispersion dielectric behavior. A relaxor-like dielectric behavior appeared around ∼475 K due to the contributions of oxygen vacancies of$(V_{\ddot{o}})$ and the $({\mathrm{Fe}}_{\mathrm{Mn}}^{\prime }-)/({\mathrm{Mn}}_{\mathrm{Fe}}^{\prime }-)$ defect dipoles. A ferrimagnetic behavior was observed in the powders at 5 K with M_S = 0.14 μ_B/f.u. and H_C = 1.51 kOe. The magnetic Curie temperature (T_C) was 381 K, whereas the Neel temperature (T_N) was 31 K. The ferrimagnetic behavior is governed by the Mn³⁺–Fe⁴⁺ double-exchange interaction via the mediated oxygen between them. The BFMO powders have a direct optical bandgap of 1.65 eV, which originates from the electron transferring from O 2p to Mn 3d (and/or Fe 3d) levels. The unique combination of high temperature ferrimagnetism and semiconductivity in the BFMO powders makes them particularly appealing for magnetic spintronics and photovoltaics.     

Fantastic valence impacts of Pr on microstructures and Faraday magneto-optical effects of transparent (Ho,Pr)2O3 ceramics

Polycrystalline magneto-optical (Ho_1-xPr_x)₂O₃ (x = 0.05?0.2) ceramics were fabricated by vacuum sintering using layered rare-earth hydroxides as the precursors, among which the 5 at.% Pr doped specimen exhibits the highest in-line transmittance of ～76.1 % at 700 nm (～94.5 % of the theoretical value of defect-free Ho₂O₃ single crystal) and the largest Verdet constant of ?82 ± 6 rad?T^?1 m^?1 at 1064 nm (～2.3 times that of the commercial Tb₃Ga₅O₁₂ crystal and ～1.8 times that of the pure Ho₂O₃ ceramic). More Pr addition not only leads to a higher thermal decomposition temperature for the precursor but also a decreasing particle size for the oxide. A 5 at.% Pr dopant in Ho₂O₃ matrix generally exists in the oxidation state of +3, while an increasing Pr concentration up to 10 at.% induces coexisting valences of +3 and +4. The grain growth was suppressed by the present Pr⁴⁺ based on interstitial mechanism. The substitution of Pr³⁺ for Ho³⁺ is helpful for the rising Verdet constant of the binary ceramic, but Pr⁴⁺ has little positive contribution to it.     

Ce3+ induced broadband enhancement around 2 μm in Tm3+/Ho3+ co-doped tellurite glass

Tellurite glasses doped with Tm³⁺, Ho³⁺ and Ce³⁺ ions were prepared via melt-quenching to realise broadband and fluorescence enhancement in near-infrared (NIR) band. Under the pumping of a commercial 808 nm laser diode (LD), the emission bands at 2.0 μm, 1.85 μm, 1.47 μm, and 705 nm were observed in the Tm³⁺/Ho³⁺ co-doping glass samples, which originated from the transitions of Ho³⁺:⁵I₇→⁵I₈ and Tm³⁺:³F₄→³H₆, ³H₄→³F₄, ³F_2,3 → ³H₆, respectively. The existence of 2.0 μm band fluorescence is due to the energy transfer from the Tm³⁺:³F₄ level to the Ho³⁺:⁵I₇ level. This band overlaps with the 1.85 μm band which forms a broadband fluorescence spectrum in the range of 1600–2200 nm. In glass samples co-doped with Tm³⁺/Ho³⁺ with 0.085 mol% Ho₂O₃ and 1 mol% Tm₂O₃, the full width at half maximum (FWHM) of this broadband spectrum (1600–2200 nm) was as high as ∼370 nm. After introducing 0.6 mol% CeO₂, the emission intensity of broadband fluorescence increased by ∼50%, which was caused by the cross-relaxations between Ce³⁺ and Tm³⁺ ions. The lifetime of fluorescence decay was determined to prove the interactions among the doped rare-earth ions, the radiative parameters such as transition probability, branching ratio and radiative lifetime were calculated from the absorption spectra based on the Judd-Ofelt theory to better understand the observed luminescence phenomena. In addition, X-ray diffraction (XRD) confirmed the amorphous state structure of the synthesised glass samples, while Raman spectrum revealed the different vibrational structural units forming the glass network.     

Structural and physical properties of Sr-based 3d–5d double perovskites of Sr2Fe0.5Hf1.5O6−δ oxides

Sr-based 3d–5d double perovskite Sr₂Fe_0.5Hf_1.5O_6−δ (SFHO) oxide powders were synthesized via the solid-state reaction method, and their structural, dielectric, magnetic, optical, and transport properties were investigated. Structural investigations revealed the SFHO powders crystallized in an orthorhombic crystal structure with Pnma space group. Scanning electron microscopy images demonstrated the relatively homogeneous distributions of spherical SFHO powders, and x-ray energy dispersive spectra gave out the molar ratio of Sr:Fe:Hf equal to 1.94:0.5:1.87, close to the nominal value. XPS spectra confirmed the existence of Sr²⁺, Fe³⁺, Hf⁴⁺ ions in the SFHO powders, and oxygen appeared in the forms of lattice oxygen and adsorbed oxygen species, respectively. The SFHO ceramics exhibited a relaxor-like dielectric behavior. Two dielectric abnormities appeared around 518 and 257 K, which were ascribed to the dielectric response of the oxygen vacancies (${\mathrm{V}}_{\mathrm{O}}^{··})\mathrm{with}$ activation energy E_a = 0.93 eV and thermal excitation of the electrons with E_a = ∼ 0.02 eV bound weakly to the${\mathrm{V}}_{\mathrm{O}}^{··}$, respectively. Ferromagnetic behavior was observed in the SFHO powders at 300 and 2 K, and the saturated magnetization at 2 K was 0.67 μ_B/f.u. Magnetic transition temperature, T_C was determined to be 638 K from the temperature dependence of the magnetization under the zero-field cooling mode. A spin glass-like behavior was observed around 390 K, which was confirmed by the frequency-dependent alternating current (ac) susceptibility measurements. The SFHO powders exhibit a butterfly-like magnetoresistance (MR)–H plot at 2 K, and the MR (2 K, 7 T) is found to be −2.73% owing to the intergranular magneto-tunneling effect. Temperature dependence of the resistivity of the SFHO ceramics displayed a semiconducting behavior, and the electrical transport properties of the SFHO ceramics were investigated by Mott's variable-range-hopping model, thermally activated semiconductor conductivity model, and the adiabatic small polarons hopping model, respectively. UV–vis diffuse-reflectance spectra of the SFHO powders demonstrated a direct optical bandgap of E_g = 2.62 eV, which was contributed from the electron transfer from the O(2p) orbital to Fe(3d)/Hf(5d) orbitals. A combination of high-temperature ferrimagnetism and semiconducting nature of the SHFO powders makes them attractive for spintronics and photovoltaics.     

Phase transition of hafnon,HfSiO4, at high pressure

The high-pressure behavior of hafnon has been systematically investigated by combining in situ synchrotron X-ray diffraction, Raman, high-resolution transmission electron microscopy (HRTEM) techniques, and theoretical simulations. Hafnon starts phase transition at 26.6 GPa and completes the transition to an irreversible scheelite phase ($I{4}_1/a$, Z = 4, a₀ = 4.712 Å, and c₀ = 10.378 Å) at ∼45 GPa. The HRTEM observation of an interface between hafnon and scheelite phases allows atomic scale understanding of the transition process with a relationship of (200)_h‖(112)_s, ${(00\overline{2})}_{\mathrm{h}}\parallel {(\overline{1}10)}_{\mathrm{s}}$//, and ${[010]}_{\mathrm{h}}\parallel {[\overline{1}\overline{1}1]}_{\mathrm{s}}$. Hafnon shows a significantly lower transition pressure (∼12.6 GPa), as calculated from the relative enthalpies, than the measured pressure (∼26 GPa), indicating a kinetically hindered process involved in the transition. A high pressure low symmetry phase in hafnon ($I{\overline{4}}_{2}d$) is identified by the simultaneous appearance of two Raman modes (∼75 and 450 cm⁻¹) at 26.6 GPa and their subsequent simultaneous disappearance at 36.7 GPa. These results are important to understanding the mechanism of the zircon-scheelite transition for both zircon and hafnon.     

Fe doping effect on EuTiO3: The magnetic properties and giant magnetocaloric effect

The magnetic properties and magnetocaloric effect for EuTi_1-xFe_xO₃ (x = 0.05, 0.1) compounds are investigated. When a part of Ti⁴⁺ions were substituted by Fe ions, the AFM ordering can be significantly changed to be FM. The EuTi_1-xFe_xO₃ (x = 0.05, 0.1) compounds exhibit a PM to FM transition with decreasing temperature and the Curie temperature is 6 K. Under the field changes of 1 T, and RC are valued to be 10.1 J/kg K and 50.2 J/kg for EuTi_0.95Fe_0.05O₃; 9.6 J/kg K and 47.7 J/kg for EuTi_0.9Fe_0.1O₃, without magnetic and thermal hysteresis. RC is almost twice as much as EuTiO₃ (27 J/kg) as substitution of Fe³⁺ ions for Ti⁴⁺ions, which may be attributed to the magnetic transition (AFM to FM). Therefore, the giant and large RC suggest the EuTi_1-xFe_xO₃ compounds are good materials for magnetic refrigerant.     

Doped tellurite glasses: Extending near-infrared emission for near-2.0-μm amplifiers

Tm³⁺-singly-doped and Tm³⁺-/Ho³⁺-codoped TeO₂-Bi₂O₃-ZnO-Li₂O-Nb₂O₅ (TBZLN) tellurite glasses were successfully prepared by the melt-quenching technique. Emission characteristics and energy transfer mechanisms were studied upon 785-nm laser diode excitation. A significant enhancement of emission intensity at 1.81 μm with increasing concentration of Tm³⁺ ions has been observed while increase in the emission intensity at 2.0 μm with increasing concentration of Ho³⁺ has been observed up to the equal concentration of Tm³⁺ (0.5 mol%) in TBZLN glasses. The stimulated emission cross section of Tm³⁺: ³F₄→³H₆ (5.20×10⁻²¹ cm²) and Ho³⁺: ⁵I₇→⁵I₈ (4.00×10⁻²¹ cm²) in 1.0 mol% Tm³⁺-doped and 0.5 mol% Tm³⁺/1.0 mol% Ho³⁺-codoped TBZLN glasses are higher compared with the reported and are found to be excellent candidates for solid-state lasers operating at ~1.8 and 2.0 μm, respectively. The extension of near-infrared (NIR) emission of Tm³⁺ with Ho³⁺ ions provides the possibility of using these materials for broadband NIR amplifiers.     

Intense emission at 2.9 μm from Yb3+/Ho3+ co-doped TeO2–Ga2O3–ZnO tellurite glasses

Mid-infrared lasers have important applications in infrared countermeasures, sensing, environmental monitoring, biomedicine, and many military and civilian fields. In this work, an intense emission at 2.9 μm from Yb³⁺/Ho³⁺ co-doped TeO₂-Ga₂O₃-ZnO (TGZ) glass was reported. The 2 μm, 1.2 μm and visible emissions were also performed to understand the competitive luminescent mechanism. With the increase in Yb³⁺ concentration, all the emissions of Ho³⁺ increased, whereas the emission of Yb³⁺ decreased due to the phonon-assisted energy transfer from Yb³⁺ to Ho³⁺. The lifetimes of optimized 3 mol% Yb₂O₃ and 1 mol% Ho₂O₃ co-doped TGZ glass, which has the maximum emission intensity, are 548 μs and 1.7 ms at 2.9 and 2 μm, respectively. The Judd–Ofelt intensity parameters, absorption, and emission cross sections were calculated to evaluate the mid-infrared fluorescence properties of this new glass matrix material. The gain coefficients show that the 2 and 2.9 μm laser gain can be realized by small pump energy, indicating that this glass is a promising medium for the mid-infrared optical fiber laser.     

Binary transparent (Ho1-xDyx)2O3 ceramics: Compositional influences on particle properties,sintering kinetics and Faraday magneto-optical effects

Binary transparent magneto-optical (Ho_1-xDy_x)₂O₃ (x = 0.01–1) ceramics derived from layered rare-earth hydroxide (LRH) compounds were fabricated by vacuum sintering. They have in-line transmittances of ～67?77 % at the visible wavelength of 700 nm and ～77?84 % at the mid-infrared wavelength of 5 μm with similar maximal infrared cut-off at ～9.5 μm. The impacts of Dy³⁺ doping on particle properties, sintering kinetics and Faraday magneto-optical effects were systematically investigated. The results show that (1) The LRH precursors exhibit the nanosheet morphology with the thickness of ～6?10 nm. Dy³⁺ incorporation not only induces an expansion for the hydroxide host layer but also a contracted interlayer distance; (2) Upon calcination at 1100 °C, the LRH nanosheets collapse into sphere-like oxide particles. The addition of Dy³⁺ leads to increasing lattice constants and decreasing theoretical densities for the (Ho,Dy)₂O₃ solid solutions; (3) A smaller bandgap energy for Dy₂O₃ (～4.85 eV) was obtained relative to those of (Ho_0.9Dy_0.1)₂O₃ (～5.24 eV) and Ho₂O₃ (～5.31 eV); (4) Dy³⁺ dopant promotes grain growth and the pure Dy₂O₃ bulk has a rather smaller grain-boundary-diffusion controlled activation energy (～457 kJ/mol) than the (Ho_0.9Dy_0.1)₂O₃ counterpart (～626 kJ/mol); (5) The Verdet constants of magneto-optical (Ho_1-xDy_x)₂O₃ ceramics generally linearly increase with the rise of Dy³⁺ concentration.     

Fabrication of 4 at.% La3+ ion doped (TbxLu0.96−x)2O3 transparent ceramics by using NC-PLSH technology and characterisation of their magneto-optical properties

Nanocrystalline powders and pressureless sintering (NC-PLSH) were used in a H₂ atmosphere to fabricate 4 at.% La³⁺ doped (Tb_xLu_0.96?x)₂O₃ magneto-optical transparent ceramics. La³⁺ was utilised as a sintering aid, and Lu³⁺ was used as a phase stabiliser. A component of the (Tb_xLu_0.96?xLa_0.04)₂O₃ magneto-optical material was designed and investigated based on powder sinterability and green compact sintering. Transparent (Tb_xLu_0.96?xLa_0.04)₂O₃ ceramics were obtained by using a one-step sintering process in H₂ atmosphere, without the need for subsequent hot isostatic pressing. The in-line transmittance of the as-polished 4 at.% La³⁺:(Tb_0.8Lu_0.16)₂O₃ ceramic was 79% at 1400 nm. The measured Verdet constant at wavelengths of 633 nm and 1064 nm was 354 rad/(T·m) and 100.2 rad/(T·m), respectively. The required length of the (Tb_0.8Lu_0.16La_0.04)₂O₃ ceramics was 63% less than that of Tb₃Ga₅O₁₂ ceramics.     

Tb3+/Yb3+ co-doped Y2O3 upconversion transparent ceramics: Fabrication and characterization for IR excited green emission

Tb³⁺/Yb³⁺ co-doped Y₂O₃ transparent ceramics were fabricated by vacuum sintering of the pellets (prepared from nanopowders by uniaxial pressing) at 1750 °C for 5 h. Zr⁴⁺ and La³⁺ ions were incorporated in Tb³⁺/Yb³⁺ co-doped Y₂O₃ nanoparticle to reduce the formation of pores which limits the transparency of ceramic. An optical transmittance of ∼80% was achieved in ∼450 to 2000 nm range for 1 mm thick pellet which is very close to the theoretical value by taking account of Fresnel’s correction. High intensity luminescence peak at 543 nm (green) was observed in these transparent ceramics under 976 and 929 nm excitations due to Yb–Tb energy transfer upconversion.     

Structural and electromagnetic properties of Ni0.5Zn0.5HoxFe2-xO4 ferrites

Ni-Zn ferrites with a nominal composition of Ni_0.5Zn_0.5Ho_xFe_2-xO₄ (x = 0–0.06) were prepared by conventional solid state reaction through using analytical-grade metal oxides powders as raw materials. The phase composition, microstructure, magnetic properties and dielectric performance of the as-prepared samples were investigated. The doped Ho³⁺ ions could enter into the crystal lattice of the resultant spinel ferrites, causing the expansion of the unit cell, reaching a saturated state when x = 0.015; and the additional Ho³⁺ ions would form a foreign HoFeO₃ phase at the grain boundary. The grain size and densification of the samples initially decreased after a small amount of Ho³⁺ ions was doped, but then increased with more Ho³⁺ ions added. The saturation magnetization decreased gradually with increasing substitution level of Ho³⁺ ions. The Curie temperature and coercivity raised initially and declined later with increasing content of Ho³⁺ ions in the samples, reaching their maximums of 305 °C with x = 0.015 and 2.99 Oe with x = 0.03, respectively. The variation of complex permeability versus Ho³⁺ ions substitution level presented an opposite trend to that of coercivity. The dielectric loss increased slightly after the introduction of a small amount of Ho³⁺ ions, but reduced significantly with more Ho³⁺ ions doped.     

Preparation of V doped lanthanum silicate electrolyte ceramics by combustion method and study on conductance mechanism

Vanadium doped La_9.33Si_6−xV_xO_26+0.5x (x = 0.5, 1.0, 1.5) (LSVO) electrolyte powder was prepared by combustion method at 600°C for 5-7 min. The powder was sintered at 1500°C for 3 hours to prepare LSVO ceramics. XPS, IR, XRD, and EIS analysis show that V⁵⁺ doping replaces Si⁴⁺ in [SiO₄] to form [Si(V)O₄] tetrahedron. With the increase in x, the lattice volume increase. When x = 2.0, the LaVO₄ phase was formed, indicating that the limit doping amount of V⁵⁺ replacing Si⁴⁺ is x ≤ 1.5. The conductivity of LSVO increases significantly with the increase in x (x ≤ 1.0), which attributed to the defect reaction caused by V⁵⁺ doping. The addition of the interstitial oxygen Oi* in 6₃ channels and the increase of lattice volume leads to increased conductivity. When x = 1.0, the highest conductivity is 1.46 × 10⁻² S·cm⁻¹ (800°C). The doping enhancement conductivity mechanism is the Interstitial oxygen defect-Lattice volume composite enhancement mechanism.     

Role of Ni2+ substituent on the structural,optical and magnetic properties of chromium oxide (Cr2-xNixO3) nanoparticles

Pristine chromium oxide (Cr₂O₃) and nickel ions (Ni²⁺) substituted Cr₂O₃ nanoparticles were synthesized using a simple co-precipitation technique. The main objective of this work is to investigate Ni²⁺ substituent's role at different concentrations on the structural, morphological, optical, and magnetic properties of Cr₂O₃ nanoparticles. Structural analyses based on X-ray diffraction (XRD), Raman and Fourier transform infra-red (FTIR) data confirmed the successful incorporation of Ni²⁺ into Cr₂O₃ nanoparticles up to x = 0.05 of Ni²⁺ content, without affecting the rhombohedral crystal structure of Cr₂O₃ nanoparticles. Rietveld refinement results showed the variation in lattice parameters and cell volumes alongwith the substitution of Ni²⁺ into Cr₂O₃ nanoparticles. Raman and FTIR spectra also depicted a considerable shift in the characteristic vibration modes of Cr₂O₃ nanoparticles due to strain-induced by Ni²⁺ substitution. Beyond x = 0.05, the structural transformation took place from rhombohedral to cubic crystal structure. Subsequently, new peaks (apart from Cr₂O₃ phase modes) have been observed at x = 0.1 of Ni²⁺ content due to the formation of secondary phase i.e., nickel chromate (NiCr₂O₄). Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) illustrated the changes in the morphology of Cr₂O₃ nanoparticles with Ni²⁺ substitution. UV–Vis analysis revealed a narrowing of optical band energy (E_g) of Ni²⁺ substituted Cr₂O₃ nanoparticles from 3 to 1.85 eV as Ni²⁺ content varies from x = 0 to 0.2, respectively. Afterward, there is an increase in optical band gap energy (E_g) when Ni²⁺ content increased from x = 0.3 to 0.5, as NiCr₂O₄ started dominating the Cr₂O₃ phase. Single-phase Ni²⁺ substituted Cr₂O₃ nanoparticles exhibited a superparamagnetic behavior, whereas the multi-phase compound ascribed to both superparamagnetic and paramagnetic. These changes in optical and magnetic properties can lead to novel strategies to render applications in the field of optoelectronics and optomagnetic devices.     

A broadband-sensitive upconverter: Garnet-type Ca3Ga2Ge3O12 codoped with Er3+, Y3+, Li+, Ni2+, and Nb5+

We have developed a new broadband-sensitive photon upconversion (UC) material that can be used for transparent ceramic plates mounted on the rear faces of crystalline silicon solar cells. We selected the host material of a cubic crystal structure codoped with Er³⁺ and Ni²⁺ so that the Ni²⁺ dopants were fully activated to sensitize the Er³⁺ emitters. In garnet-type Ca₃Ga₂Ge₃O₁₂ with additional codopants of Nb⁵⁺ and Li⁺ for charge compensation, all the Ni²⁺ dopants occupied the six-coordinated Ga³⁺ sites, leading to highly efficient energy transfer from the Ni²⁺ to the Er³⁺. Formation of four-coordinated Ni²⁺ that quenches the UC emission of the Er³⁺ was prevented, because Ni²⁺ cannot substitute the four-coordinated Ge⁴⁺ much smaller than Ni²⁺. Consequently, energy dissipation from the Er³⁺ to the Ni²⁺ was well reduced compared with the previously developed Gd₃Ga₅O₁₂:Er,Ni,Nb in which the Ni²⁺ dopants partially occupied the four-coordinated Ga³⁺ sites. Additional introduction of Y³⁺ and Li⁺ enhanced optical transitions and improved the UC performance, owing to more enhanced lattice distortion, along with eliminating different phases. The optimal composition (Ca_0.6Er_0.1Y_0.1Li_0.2)₃(Ga_0.98Ni_0.01Nb_0.01)₂Ge₃O₁₂ exhibited a broadband sensitivity ranging from 1.1 μm (the absorption edge of silicon) to 1.6 μm for the UC emission at 0.98 μm.     

Exploring the luminescence of tin-incorporated nickel-sensitized lithium gallate short-wave-infrared phosphors

A series of Ni²⁺-sensitized LiGa₅O₈ nanocrystals doped with varying amounts of Sn⁴⁺ were synthesized via a high-temperature solid-state method. X-ray diffraction and scanning electron microscopy were employed to investigate the microstructure of the LiGa₅O₈ host, and optical spectroscopy was used to examine the effects of Sn⁴⁺ addition on the emission spectra and persistent luminescence (PersL) properties, which indicated a homogeneous distribution of the constituent elements in the phosphor. The Sn⁴⁺ incorporation led to an approximately sixfold enhancement of photoluminescence intensity at room temperature and decrease in the energy transition of Ni²⁺(³T₂(³F)→³A₂(³F)), which resulted in ∼65 nm bathochromic shift in the photoluminescence emission maxima. However, the addition of Sn⁴⁺ dopant led to a decrease in the quantum yield of luminescence compared to that of the original phosphor. Temperature-dependent thermoluminescence measurements revealed that doping of LiGa₅O₈ with Sn⁴⁺ interfered with the Ni²⁺ trap centers. Moreover, Ni²⁺-sensitized Sn⁴⁺-doped LiGa₅O₈ nanocrystals exhibited an afterglow effect that persisted for up to 300 s.     

Highly active and robust biomimetic ceramic catalyst for oxygen reduction reaction: Inspired by plant leaves

Structural instability under working conditions is critical issue that restricts applications of perovskite O₂ catalysts in the field of solid oxide fuel cells. Inspired by plant leaves, a biomimetic ceramic catalyst with PrBaCo₂O_5+δ ‘mesophyll’ and Gd_0.1Ce_0.9O_1.95 ‘epidermis’ and ‘vein’ was successfully engineered in this work. The ‘epidermis’ reduces the polarization resistance of O₂ reduction reaction on catalyst surface by ∼24%, and the ‘vein’ reduces resistance of O²⁻ transport through cathode layer by ∼65%. Moreover, this biomimetic catalyst increases output power density of the cell by 79% and reverses rapid decay trend of the cell with a 23% increase in power density during first 20 h followed by stabilization at 0.91 W cm⁻² (at 750 °C and 0.7 V). This discovery provides new avenue for the development of high-performance O₂ catalysts with practical applications and enriches the scientific understanding of catalysis.