Preparation and optical properties of Er<Superscript>3+</Superscript>: Na<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> transparent glass-ceramics

Na₂O-Al₂O₃-SiO₂ glass-ceramics doped with Er³⁺ ions were synthesized by the conventional melt quenching technique at a low melting temperature. The samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis-NIR scanning spectrophotometry, and fluorescence spectrometry. The results show that the main crystalline phase of glass-ceramics is nepheline.The best heat-treatment process is at 520 °C for 2 h. Because the up-conversion luminescence and near infrared luminescence properties of glass doped with Eu³⁺ are studied in detail.     

Preparation and Upeonversion Lumineseenee ofNanoerystailine Gd2O3： Er^3＋, Yb^3＋

Nanocrystalline Gd1.77Yb0.2Er0.03O3 samples were prepared by combustion and precipitation methods. Structures and upconversion luminescence properties of samples were studied. The results of XRD show that all samples are cubic structure, the average crystallite size could be calculated as 23 nm and 39 nm, respectively. The lattice constants were obtained. The FT-IR spectra were measured to investigate the vibrational feature of the samples. Upconversion luminescence spectra of samples under 980 nm laser excitation were investigated. The strong red emission of samples were observed, and attributed to 4F9/2→4I152 transitions of Er^3＋ ions, the emission intensity for sample synthesized by precipitation method is stronger compared to that of combustion method. The possible upconversion luminescence mechanisms in nanocrystalline Gd1.77Yb0.2Er0.03O3 were discussed.     

Interaction of rare earth ions in Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> material

To discuss the function of Eu and Dy and their interaction in Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ long afterglow material, the Eu and Dy single doped and their co-doped Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ were prepared. The samples were characterized by X-ray diffraction (XRD), decay curves, photoluminescence (PL), and thermoluminescence (TL). The results indicate that Sr₂MgSi₂O₇: Eu has afterglow properties, and the doping of Eu ion in Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ can lower the depth of traps. Eu ion can not only serve as luminescence center, but also produce traps in the matrix, meanwhile, it also exerts certain influences on the traps produced by Dy in Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺. The Dy ion can not act as luminescence center but relates to the change of the traps in the Sr₂MgSi₂O₇ matrix.     

Fluorescence detection for H<Subscript>2</Subscript>PO<Subscript>4</Subscript><Superscript>-</Superscript> based on carbon dots/Fe<Superscript>3+</Superscript> composite

A novel fluorescent probe for H₂PO₄ ^- was designed and fabricated based on the carbon dots/Fe³⁺ composite. The carbon dots were synthesized by an established one-pot hydrothermal method and characterized by transmission electron microscope, X-ray diffractometer, UV-Vis absorption spectrometer and fluorescence spectrophotometer. The carbon dots/Fe³⁺ composite was obtained by aqueous mixing of carbon dots and FeCl₃, and its fluorescence property was characterized by fluorescence spectrophotometer. The fluorescence of carbon dots was quenched by aqueous Fe³⁺ cations, resulting in the low fluorescence intensity of the carbon dots/Fe³⁺ composite. On the other hand, H₂PO₄ ^- reduced the concentration of Fe³⁺ by chemical reaction and enhanced the fluorescence of the carbon dots/Fe³⁺ composite. The Stern-Volmer equation was introduced to describe the relation between the relative fluorescence intensity of the carbon dots/Fe³⁺ composite and the concentration of H₂PO₄ ^-, and a fine linearity (R ²=0.997) was found in the range of H₂PO₄ ^- concentration of 0.4-12 mM.     

Phase transition and photoluminescence properties of Eu<Superscript>3+</Superscript>-doped ZnMoO<Subscript>4</Subscript> red phosphors

Eu³⁺-doped ZnMoO₄ with different doping concentrations were synthesized by a hydrothermal method. The effects of Eu³⁺ doping on the phase structure and photoluminescence (PL) properties of ZnMoO₄ were investigated. The result showed that the introduction of Eu3+ could lead to phase transition of ZnMoO₄. With the increase of Eu³⁺ doping amount, β-ZnMoO₄ was transformed to α phase gradually, which led to different photoluminescence performances. The optimized doping concentration of Eu³⁺ was 6 mol% for the highest emission intensity at 615 nm. Its CIE chromaticity coordinates were (0.667, 0.331), which were very close to the values of standard chromaticity (0.67, 0.33) for National Television Standards Committee (NTSC) system. Therefore, Eu³⁺-doped ZnMoO₄ is considered to be a promising red-emitting phosphor for white LED applications.     

Synthesis of M (M=Co<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>/Ni<Superscript>2+</Superscript>)-doped FeS<Subscript>2</Subscript> Nanospheres with Enhanced Visible-light-induced Photocatalytic Activity

Nano-spherical Co²⁺-doped FeS₂ was synthesized through a simple solvothermal method. The products were investigated using XRD, FE-SEM, BET, ICP, EDS, TEM, HRTEM, XPS, and UV-vis spectroscopy. The results indicated that Co²⁺ ion could change the particle nucleation process and inhibited the particle growth of FeS₂. In addition, when the content of doped Co²⁺ was 15%, the degradation efficiency of methylene blue (MB) achieved 60.72% after 210 min irradiation, which increased by 52.01% than that of the undoped FeS₂. Moreover, comparison experiments also demonstrated that the M (M=Co²⁺, Co²⁺/Ni²⁺)-doped FeS₂ photocatalytic activity efficiency sequence was Co²⁺ > Ni²⁺>Co²⁺/Ni²⁺. This is ascribed to the fact that the Co²⁺ doping could induce the absorption edge shifting into the visible-light region and increased the surface area of the samples. The effect mechanisms of M-doping on the band gap and the photocatalytic activity of FeS₂ were also discussed.     

Frequency up-conversion luminescence properties and mechanism of Tm<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped oxyfluorogermanate glasses

Oxyfluoride glasses were developed with composition 60GeO 2 ·10AlF 3 ·25BaF 2 ·(1.95-x)GdF 3 · 3YbF 3 ·0.05TmF 3 ·xErF 3 (x=0.02,0.05,0.08,0.11,0.14,0.17)in mole percent.Intense blue(476 nm),green(524 and 546 nm)and red(658 nm)emissions which identified from the 1G 4 →3H 6 transition of Tm3+and the(2H 11/2 ,4S 3/2 )→4I 15/2 ,4F 9/2 →4I 15/2 transitions of Er3+,respectively,were simultaneously observed under 980 nm excitation at room temperature.The results show that multicolor luminescence including white l...     

Synthesis and luminescence of nano fluorescent powder of Y<Subscript>4</Subscript>Al<Subscript>2</Subscript>O<Subscript>9</Subscript>: Eu<Superscript>3+</Superscript>

Nano fluorescent powder of Y₄Al₂O₉: Eu³⁺ was synthesized by sol-gel method. The XRD shows that the product prepared at 900°C is pure-phase Y₄Al₂O₉: Eu³⁺. The Y₄Al₂O₉ powder is nano-size crystal testified by BF and ED analysis of TEM. The grain diameter of Y₄Al₂O₉ is in the range between 20 and 50nm, and its average is 30 nm. The luminescent spectra show that Eu³⁺ ious occupy two kinds of sites in Y₄Al₂O₉ crystal lattice. One is in the strict inversion center, and the other is in off lying inversion center. When excited with UV light (λ=254nm), Y₄Al₂O₉: Eu³⁺ exhibits an orange emission bond at λ=590 nm due to the⁵D_o→⁷F₁ transition and a red emission band at λ=610 nm due to⁵D_o→⁷F₂ transition. YUAN Xi-ming: Born in 1951 Funded by Key Scientific and Technological Project of Hubei Province (2001 AA102A03)     

Roles of Eu^2＋, Dy^3＋ Ions in Persistent Luminescence of Strontium Aluminates Phosphors

The polycrystalline Eu^2＋ and Dy ^3＋ co-doped strontium aluminates SrAl2O4： Eu^2＋, Dy^3＋ with different compositions were prepared by solid state reactions. The UV-excited photoluminescence, persistent luminescence and thermo-luminescence were studied and compared. Results show that the doped Eu^2＋ ion in SrAl2O4： Eu^2＋, Dy^3＋ phosphors works as not only the UV-excited luminescent center but also the persistent luminescent center. The doped Dy^3＋ ion can hardly yield any luminescence under UV-excitation, but effectively enhance the persistent luminescence and thermo-luminescence of SrAl2O4： Eu^2＋. Dy^3＋ co-doping can help form electron traps with appropriate depth due to its suitable electro-negativity, and increase the density and depth of electron traps. Based on above observations, a persistent luminescence mechanism, electron transfer model, is proposed and illustrated.     

Phase Structure and Dielectric Properties of Doped BaTiO3 Ceramics

The effects of two rare earth oxides such as CeO2 and Sm2O3 on the phase structure and dielectric properties of BaTiO3 ceramic were investigated. Results indicate that the dielectric constant of this system will increase greatly with the increasing content of these two oxides, and Ce^4＋ substitutes for Ba^2＋ located at A-site in ABO3 structure. Quantitative XRD analysis shows that c/a ratio in the sample with addition of CeO2 will increase, which implies the increase of tetragonality in system, causing the augment of dielectric constant, and the decrease of the crystal＇s geometrical symmetry results in curie-temperature moving towards low temperature; Sm^3＋（0.096 nm） substitutes for Ba^2＋（0.135 nm） possessing larger radius in A-site and the electrovalency in A-site increases, the mutual effect is strengthened, so the polarization is enhanced, and the dielectric constant increases notablely.     

Phase structure and electrical properties of La<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped BiInO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ceramics with high curie temperature

The phase structure and electrical properties of pure and La2O3-doped Bi-InO3-PbTiO3 （BI-PT） ceramics were studied respectively. In （1 -x）BI-xPT （x=0.72-0.80） ceramics, the stability of tetragonal phase increased with increasing x, and pure perovskite structure was obtained for x=-0.80 ceramics. The phase transition temperature range was between 575 ℃ and 600 ℃ for x=0.72-0.80 ceramics, higher than that of PT （-490 ℃）. The c/a ratio almost linearly decreased with increasing La2O3 content in x-0.80 ceramics. It is believed that Pb^2＋ vacancies were formed by La^3＋ substituting Pb^2＋ in La2O3-doped BI-PT ceramics. Tc shifted to lower temperature by 30 ℃/mol% La2O3. The maximum dielectric constant 8557 around 559 ℃ was exhibited in 0.5mol%-doped BI-0.80PT ceramics. La2O3-doped ceramics could be poled resulting from decreasing of c/a ratio and improving of dielectric loss and resistivity. The maximum piezoelectric coefficient d33 was 12 pC/N for 2mol%-doped BI-0.80PT ceramics.     

Resistive switching behavior of Ag/Mg<Subscript>0.2</Subscript>Zn<Subscript>0.8</Subscript>O/ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/p<Superscript>+</Superscript>-Si heterostructure devices for nonvolatile memory applications

The Ag/Mg_0.2Zn_0.8O/ZnMn₂O₄/p⁺-Si heterostructure devices were fabricated by sol-gel spin coating technique and the resistive switching behavior, conduction mechanism, endurance characteristic, and retention properties were investigated. A distinct bipolar resistive switching behavior of the devices was observed at room temperature. The resistance ratio R _HRS/R _LRS of high resistance state and low resistance state is as large as four orders of magnitude with a readout voltage of 2.0 V. The dominant conduction mechanism of the device is trap-controlled space charge limited current (SCLC). The devices exhibit good durability under 1×10³ cycles and the degradation is invisible for more than 10⁶ s.     

Low temperature synthesis of amorphous La<Subscript>0.7</Subscript>Zn<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> films grown on p<Superscript>+</Superscript>-Si substrates and its resistive switching properties

Amorphous La_0.7Zn_0.3MnO₃ (LZMO) films were deposited on p⁺-Si substrates by sol-gel method at low temperature of 450 °C. The Ag/LZMO/p⁺-Si device exhibits invertible bipolar resistive switching and the R _HRS/R _LRS was about 10⁴-10⁶ at room temperature which can be kept over 10³ switching cycles. Better endurance characteristics were observed in the Ag/LZMO/p⁺-Si device, the V _Set and the V _Reset almost remained after 10³ endurance switching cycles. According to electrical analyses, the conductor mechanism was in low resistor state (LRS) governed by the filament conductor and in the high state (HRS) dominated by the traps-controlled space-charge-limited current (SCLC) conductor.     

Enhanced Ferroelectric Polarization in Laser-ablated Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films by Controlling Preferred Orientation

Polycrystalline Bi₄Ti₃O₁₂ thin films with various fractions of a-axis, c-axis and random orientations have been grown on Pt(111)/Ti/SiO₂/Si substrates by laser-ablation under different kinetic growth conditions. The relationship between the structure and ferroelectric property of the films was investigated, so as to explore the possibility of enhancing ferroelectric polarization by controlling the preferred orientation. The structural characterization indicated that the large growth rate and high oxygen background pressure were both favorable for the growth of non-c-axis oriented grains in the Bi₄Ti₃O₁₂ thin films. The films with high fractions of a-axis and random orientations, i e, f (a-sxis) = 28.3% and f (random) = 69.6%, could be obtained at the deposition temperature of 973 K, oxygen partial pressure of 15 Pa and laser fluence of 4.6 J/cm², respectively. It was also noted that the variation of ferroelectric polarization was in accordance with the evolution non-c-axis orientation. A large value of remanent polarization (2Pr = 35.5 μC/cm²) was obtained for the Bi₄Ti₃O₁₂ thin films with significant non-c-axis orientation, even higher than that of rare-earth-doped Bi₄Ti₃O₁₂ films.     

Effect of Constituent Core-sizes on Microstructure and Dielectric Properties of BaTiO<Subscript>3</Subscript>@(0.6Ba-TiO<Subscript>3</Subscript>-0.4BiAlO<Subscript>3</Subscript>) Core-Shell Material

The fundamental characteristics of varied initial core-sizes of BaTiO₃(BT) and its influential role on the morphology and dielectric properties of BaTiO₃@0.6BaTiO₃-0.4BiAlO₃(BT@0.6BT-0.4BA) ceramic samples were studied. Alkoxide sol-precipitation method was adopted as revised chemical route to synthesize the constituent “core” BT powders in a dispersed phase, whereas the distinctive initial nano-sized particles were affected by the pre-calcination temperatures (600-900 °C).The microstructure of the uncoated BT ceramics revealed an exaggerated grain growth with an optimized dielectric constant (ε_max >9 000) whilst the coated ceramics behaved otherwise (grain growth inhibited) when sintered at an elevated temperature. Regardless of the previously studied solubility limit (about 0.1%) of BT-BA samples, BT@0.6BT-0.4BA maintained a maximum dielectric constant (ε_max) ranging from 1 592 to 1 708 and tan δ less than 2% under a unit mole ratio at room temperature. In view of all these analyses, the initial nanometer sizes of the as-prepared BT-core powders combined with the increase effect of cation substitutions of Bi³⁺ and Al³⁺ in the shell content, induced the diffuse transition phase of BT@0.6BT-0.4BA composition.     

Preparation of nanometer Nd<Superscript>3+</Superscript>, Y<Superscript>3+</Superscript> co-doped CaF<Subscript>2</Subscript> powder by coprecipitation-azeotropic distillation technique

The synthesis of Nd³⁺, Y³⁺:CaF₂ nanopowder was conducted by azeotropic distillation method, which effectively dehydrated hydrous CaF₂ and prevented forming hard agglomerates. X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning calorimetries-thermalgravimetry (DSC-TG), Fourier transform infrared spectroscopy (FT-IR) and absorption spectroscopy were performed to characterize the powder properties. The experimental results showed that products obtained by azeotropic distillation were single phased, rather monodispersed, successfully prevented the hard agglomerate formation and effectively removed the residual water inside the as-prepared precipitate than that of the direct drying. The absorption spectra showed a wider and stronger absorption bands around 792 nm, which should be profitable for LD pumping.     

The phase transformation of R<Subscript>2</Subscript>O-CaO-SiO<Subscript>2</Subscript>-F glass-ceramics

The phase transformation of R₂O-CaO-SiO₂-F system glass-ceramics with various additions of K₂O and F was investigated by DTA, XRD, SEM and other techniques. The crystallization and the microstructure of the obtained glass-ceramics were also evaluated. The phase separation occurred in CN1 specimen after being quenched in water, but phase separation did not appear in other quenched specimens with the content of K₂O and F increasing obviously, showing K₂O and F modified the structure of the glass-forming melts. The increase of K₂O and F resulted in the reduction of phase separation and the enhancement of crystallization. The main crystalline phase formed after heat-treatment was canasite and CaF₂. The microstructures of the crystalline specimens consisted of interlocking radial and granular crystals. Moreover, the crystallinity was increased as the content of K₂O was increased from 0.07 mol to 0.08 mol.     

Microstructures and fatigue-free properties of the La<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by modified sol-gel technique

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) and Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were fabricated on Pt/TiO₂/SiO₂/Si (100) substrates by a modified sol-gel technique. X-ray diffraction indicated that these films were of single phase with random polycrystalline orientations. The surface morphologies of the films were observed by scanning electron microscope, showing uniform, dense films with grain size of 50–100 nm. Well-saturated hysteresis loops of the films were obtained in metal-ferroelectric-metal type capacitors with Cu top electrodes at an applied voltage of 400 kV/cm, giving the remanent polarization (2P _r) and coercive field (2E _c) values of the films of 25.1 μC/cm² and 203 kV/cm for BLT, and 44.2 μC/cm² and 296 kV/cm for BNT, respectively. Moreover, these capacitors did not show fatigue behaviors after up to 1.75×10¹⁰ switching cycles at the test frequency of 1 MHz, suggesting a fatigue-free character. The influences of the La³⁺ and Nd³⁺ doping on the properties of the films were comparatively discussed. Supported by the National Key Basic Research and Development Program of China (Grant No. 2006CB932305) and the Natural Science Foundation of Hubei Province, China (Grant No. 2004ABA082)     

Crystal growth,structure and properties of bismuth triborate BiB<Subscript>3</Subscript>O<Subscript>6</Subscript> crystal

BiB₃O₆ (BIBO) single crystals with size of 46×23×10 mm³ and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB₃O₆ is C2 and the cell parameters are a=7.1203(7) Å, b=4.9948(7) Å, c=6.5077(7) Å, β=105.586(8)″, and V=222.93(5) ų. The density of BIBO is 4.8965 g/cm³. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB₃O₆ is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB₃O₆ is a kind of excellent nonlinear optical (NLO) crystal.     

Optimized photoluminescence of red phosphor K<Subscript>2</Subscript>LiAlF<Subscript>6</Subscript>:Mn<Superscript>4+</Superscript> synthesized by a cation-exchange method

Red phosphor K₂LiAlF₆:Mn⁴⁺ has been synthesized by a cation-exchange method in HF solution. To optimize their optical properties, phosphors were synthesized using different reaction conditions. The K₂LiAlF₆:0.5%Mn⁴⁺ synthesized at 20°C for 4 h shows the highest luminescence intensity. The temperature-dependent emission intensity of the phosphor was investigated, and it was found to exhibit good thermal stability, making it a promising red phosphor candidate for warm WLEDs.