Eu3+-Doped (Gd, La)AlO3 Perovskite Single Crystals: Growth and Red-Emitting Luminescence.

Eu3+-doped GdAlO3 (Eu:GAP) and Gd0.5La0.5AlO3 (Eu:GLAP) perovskite single crystals were successfully grown using the optical floating zone (OFZ) method. The microstructure, optical, photoluminescence (PL) and radioluminescence (under X-ray excitation, XEL) were investigated. Under the PL excitation of 275 nm, obvious emission bands peaking at 556 nm, 592 nm, 617 nm, 625 nm, 655 nm, and 706 nm were demonstrated, which correspond to the 5D0 → 7Fj (j = 0-4) transitions of Eu3+. The grown Eu:GAP single crystal showed a stronger PL intensity compared with that of Eu:GLAP in the red light region. After annealing at 1000 °C for 4 h in weak reductive atmosphere (Ar + 5% H2), a slight redshift and dramatic enhancement of PL and XEL intensity occurred. In addition, Eu:GLAP show a more intense XEL emission than that of Eu:GAP. Considering their different densities, these two kinds of red luminescence phosphors are proposed to be promising in a wide field of X-ray imaging, warm white, or plant lighting, respectively.

1D and 3D co-simulation and self-adaptive position control of electrostatic levitation in China's Space Station.

The greatest challenge of electrostatic levitation for containerless material processing is the stable control of charged material during heating. Recently, high-precision self-adaptive control of electrostatic levitation has been achieved in China's Space Station. Based on the 1D and 3D co-simulation analysis, an optimal scheduling of control strategies of sample release and retrieval in space is developed. Both simulation results and on-orbit experiments demonstrated that the inversion of surface charge is responsible for the heating induced material instability. On-orbit experiments indicated that under laser illuminations, the net surface charge of metal Zr changed from positive to negative at 900 K and from negative to positive at 1300 K. The possible physical mechanism of the charge inversion of heated material is discussed.

Crystal growth engineering and origin of the weak ferromagnetism in antiferromagnetic matrix of orthochromates from t-e orbital hybridization.

We report a combined experimental and theoretical study on intriguing magnetic properties of quasiferroelectric orthochromates. Large single crystals of the family of RECrO3 (RE = Y, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) compounds were successfully grown. Neutron Laue study indicates a good quality of the obtained single crystals. Applied magnetic field and temperature dependent magnetization measurements reveal their intrinsic magnetic properties, especially the antiferromagnetic (AFM) transition temperatures. Density functional theory studies of the electronic structures were carried out using the Perdew-Burke-Ernzerhof functional plus Hubbard U method. Crystallographic information and magnetism were theoretically optimized systematically. When RE3+ cations vary from Y3+ and Eu3+ to Lu3+ ions, the calculated t-e orbital hybridization degree and Néel temperature behave similarly to the experimentally determined AFM transition temperature with variation in cationic radius. We found that the t-e hybridization is anisotropic, causing a magnetic anisotropy of Cr3+ sublattices. This was evaluated with the nearest-neighbor J 1-J 2 model. Our research provides a picture of the electronic structures during the t-e hybridization process while changing RE ions and sheds light on the nature of the weak ferromagnetism coexisting with predominated antiferromagnetism. The available large RECrO3 single crystals build a platform for further studies of orthochromates.

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

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

Analysis of electrostatic levitation control system and oscillation method for material properties measurement.

Electrostatic levitation is an important method of studying material properties. Without using a container, a physical object is levitated between electrostatic plates and melted to the liquid state using a laser. Then, measurements are made via fast cooling or oscillation. Control technology is critical to the electrostatic levitation system. Uncertainty regarding the sample charge during the start-up and laser-melting periods often causes disturbances or causes levitation to fail. In this paper, we design a two-step adaptive control strategy with charge estimation and feed-forward control. This method can better adapt to charge uncertainty during the initial stage. In addition, we propose an innovative new method of superimposing oscillation signals via software to measure the material surface tension and viscosity. Unlike the traditional method, this approach does not require extra hardware resources and is flexible with regard to regulating the frequency and amplitude. A control system model with an accurate electric field model is established and used to simulate control progress in order to illustrate the advantage of our control method. Experiments based on a high-speed vision-servo system also validate the effectiveness of the adaptive and oscillation control strategies.

Large Polarization Switching and High-Temperature Magnetoelectric Coupling in Multiferroic GaFeO3 Systems.

GaFeO3-type iron oxides are promising multiferroics due to the coexistence of large spontaneous magnetization and polarization near room temperature. However, the high leakage current and difficulties associated with synthesizing single crystals make it difficult to achieve two important features in the system: a large ferroelectric polarization switching and magnetoelectric coupling at a high-temperature region. Herein, we report successful achievement of these features by preparing high-quality Sc-doped GaFeO3 single crystals (ScxGa1-x/2Fe1-x/2O3 with x = 0-0.3) using the floating zone method. The x ≥ 0.05 crystals exhibit a leakage current 104 times lower than the x = 0 crystals, highlighting the importance of Sc doping. Because of the reduced leakage current, the Sc-doped crystals exhibit large ferroelectric polarization switching along the c-axis with a remanent polarization of 22-25 µC/cm2, which is close to the theoretically predicted polarization value of 25-28 µC/cm2. In addition, the Sc-doped crystals exhibit ferrimagnetism with magnetic anisotropy along the a-axis. Furthermore, a magnetic-field-induced modulation of polarization is observed in the x = 0.15 crystal even at a relatively high temperature, i.e., 100 K.

Homogeneous InGaSb crystal grown under microgravity using Chinese recovery satellite SJ-10.

Microgravity crystal growth experiment for the growth of In0.11Ga0.89Sb was performed at the Chinese recoverable satellite through the space program SJ-10. This experiment is aimed to understand the melt formation and growth kinetics of In x Ga1-x Sb solid solution with higher indium composition, because their segregation coefficient was higher than the crystals with lower indium compositions. The target composition and uniformity were achieved with higher growth rate under microgravity, whereas the uniformity in composition was not achieved under normal gravity. The growth and dissolution were affected mainly by the steady state equilibrium in the melt composition because of the convection under normal gravity. The non-steady state equilibrium in the melt composition under microgravity helped to achieve a higher growth rate and compositional homogeneity at higher indium composition of In x Ga1-x Sb solid solution.

Study on Upconversion and Thermal Properties of Tm3+/Yb3+ Co-Doped La2O3-Nb2O5-Ta2O5 Glasses.

The effect of Yb3+ ions on upconversion luminescence and thermal properties of Tm3+/Yb3+ co-doped La2O3-Nb2O5-Ta2O5 glasses has been studied. Glass transition temperature is around 740 °C, indicating high thermal stability. The effect of Yb3+ ions on the thermal stability is not obvious. Both the glass forming ability and the upconversion luminescence first increase and then decrease with the increase of Yb3+ ions. The glasses perform low glass forming ability with ΔT around 55 °C. Blue and red emissions centered around 477, 651, and 706 nm are obtained at the excitation of 976 nm laser. The upconversion luminescence mechanism is energy transfer from Yb3+ to Tm3+ mixed with two- and three- photon processes. The thermal kinetic Differential Thermal Analysis (DTA)-analysis indicates that the average activation energy first increases and then decreases with the increase of Yb3+ ions. This result can be introduced in order to improve upconversion luminescence of glasses by crystallization in the future. Tm3+/Yb3+ co-doped La2O3-Nb2O5-Ta2O5 glasses with good upconversion and thermal properties show promising applications in solid-state laser, optical temperature sensing.

Large magnetoelectric coupling in magnetically short-range ordered Bi5Ti3FeO15 film.

Multiferroic materials, which offer the possibility of manipulating the magnetic state by an electric field or vice versa, are of great current interest. However, single-phase materials with such cross-coupling properties at room temperature exist rarely in nature; new design of nano-engineered thin films with a strong magneto-electric coupling is a fundamental challenge. Here we demonstrate a robust room-temperature magneto-electric coupling in a bismuth-layer-structured ferroelectric Bi5Ti3FeO15 with high ferroelectric Curie temperature of ~1000 K. Bi5Ti3FeO15 thin films grown by pulsed laser deposition are single-phase layered perovskit with nearly (00l)-orientation. Room-temperature multiferroic behavior is demonstrated by a large modulation in magneto-polarization and magneto-dielectric responses. Local structural characterizations by transmission electron microscopy and Mössbauer spectroscopy reveal the existence of Fe-rich nanodomains, which cause a short-range magnetic ordering at ~620 K. In Bi5Ti3FeO15 with a stable ferroelectric order, the spin canting of magnetic-ion-based nanodomains via the Dzyaloshinskii-Moriya interaction might yield a robust magneto-electric coupling of ~400 mV/Oe·cm even at room temperature.

Stabilization of metastable ferroelectric Ba1-xCaxTi2O5 by breaking Ca-site selectivity via crystallization from glass.

The thermal stability and dielectric and structural properties of ferroelectric Ba1-xCaxTi2O5 (0 ≤ x ≤ 0.30) prepared by crystallization from glass are investigated. The Ba1-xCaxTi2O5 compounds with x < 0.10 are thermally stable phases, while those with x ≥ 0.10 are metastable phases. The ferroelectric transition temperature drastically decreases from 470 to 220°C with increasing x. Crystal structure analyses reveal that one of two possible Ba sites is occupied by Ca in the stable phase region, while Ca-site selectivity is broken in the metastable phase region. The Ca-site selectivity introduces local distortion and makes the crystal lattice unstable. However, the local distortion is suppressed by the occupancy of Ca into both Ba sites. Accordingly, the metastable ferroelectric phase can be obtained beyond the substitution limit of Ca by crystallization from the glassy state. The stabilization mechanism provides possible wide control of the functionality of materials by expanding the composition range.

Containerless processing for preparation of akermanite bioceramic spheres with homogeneous structure, tailored bioactivity and degradation.

Bioceramic spheres have been widely studied for bone/dental filler materials. Conventional methods, such as alginate cross-linking, microemulsion and spray drying, have distinct disadvantages for preparing pure bioceramic spheres with controllable size, bioactivity and degradation. In this study, a containerless processing method, for the first time, was applied to prepare bioceramic spheres for potential bone/dental filling applications. Akermanite (Ca2MgSi2O7, AKT) glass spheres were firstly prepared by a unique containerless processing method. Then, the as-prepared AKT glass spheres were heat-treated at varied temperatures. Furthermore, the effect of heat treatment on the phase transition, surface microstructure, apatite mineralization and ionic dissolution production of AKT spheres has been systematically studied. The interaction of MC3T3 cells with AKT spheres was further studied by investigating cell attachment, proliferation and alkaline phosphate (ALP) activity. The results show that containerless processing is a quite effective method to prepare homogeneous AKT glass spheres with controllable size. Heat-treatment promotes the phase transition from amorphous, semi-crystalline to fully crystalline AKT spheres. Thus, AKT spheres with controllable crystallinity were successfully prepared by combining containerless processing and heat treatment. The as-prepared AKT glass spheres induced apatite mineralization after soaking in simulated body fluids (SBF) for 7 days; however, AKT spheres treated at 800 °C suppressed apatite mineralization in SBF. Interestingly, AKT spheres treated at 1000 or 1350 °C had distinct apatite mineralization, indicating that the bioactivity of the AKT spheres can be regulated by modulating the heat-treatment-induced crystallinity. Further study has shown that the ionic dissolution production of the containerless-processed AKT spheres can be tailored by controlling the heat-treatment temperatures. The prepared crystalline AKT spheres supported the attachment, spreading, growth and early differentiation of MC3T3 cells, and significantly stimulated the proliferation of MC3T3. Therefore, the containerless-processed AKT spheres may be a unique bone/dental filler material due to their homogeneous structure, controllable size, bioactivity and ionic degradation, as well as their excellent cytocompatibility.

Property measurements and solidification studies by electrostatic levitation.

The National Space Development Agency of Japan has recently developed several electrostatic levitation furnaces and implemented new techniques and procedures for property measurement, solidification studies, and atomic structure research. In addition to the contamination-free environment for undercooled and liquid metals and semiconductors, the newly developed facilities possess the unique capabilities of handling ceramics and high vapor pressure materials, reducing processing time, and imaging high luminosity samples. These are exemplified in this paper with the successful processing of BaTiO(3). This allowed measurement of the density of high temperature solid, liquid, and undercooled phases. Furthermore, the material resulting from containerless solidification consisted of micrometer-size particles and a glass-like phase exhibiting a giant dielectric constant exceeding 100,000.