White light emitting from YVO4/Y2O3:Eu3+,Bi3+ composite phosphors for UV light-emitting diodes

A series of (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 (0≤x≤0.54) composite phosphors was synthesized in one step by high temperature solid state reaction and the photoluminescence properties were investigated. By means of co-doping Eu³⁺ and Bi³⁺ ions into the composite matrices composed of YVO₄ and Y₂O₃ crystals, the YVO₄/Y₂O₃:Eu³⁺,Bi³⁺ phosphor exhibits simultaneously the blue (418 nm), green (540 nm) and orange-red (595, 620 nm) emissions. The broad blue and green emissions are attributed to the ³P₁–¹S₀ transitions of Bi³⁺ ion both in Y₂O₃ and in YVO₄ matrices. Moreover, the sharp orange-red emissions are attributed to the ⁵D₀–⁷F_1,2 transitions of Eu³⁺ ion in YVO₄ matrix. By tuning the mole ratio of YVO₄/Y₂O₃ matrices the white light-emitting could be obtained. The results indicated that when the mole ratio of Y₂O₃ (x) is at 0.11–0.54 mol, the (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 phosphors emit white light by combining the blue, green and orange-red emissions under the excitation of 360–370 nm wavelength which matches the emission of the commercial UV-LED diode. This implies that the phosphors may be the promising white light materials with broad absorption band for white light-emitting diodes.     

Novel amorphous precursor densification to transparent Nd:Y2O3 Ceramics

A novel approach of neodymium ion doped yttrium oxide (Nd:Y₂O₃) amorphous precursor compaction and sintering is being reported for the first time. Precursor of 2 at.% Nd³⁺ doped Y₂O₃ was synthesized by gelation of sol of yttrium and neodymium nitrates with l-alanine at 80 °C for 16 h followed by gel combustion in microwave. A part of microwave precursor was heat treated at 700 °C for 5 h to give the partially crystalline Nd:Y₂O₃ amorphous precursor. Thermogravimetric analysis (TGA) of partially crystalline amorphous precursor of Nd:Y₂O₃ gave 8.5% total weight loss indicating removal of maximum organics. X-Ray diffraction (XRD) showed broad peaks indicating incomplete crystallization of cubic Nd:Y₂O₃. Morphology was found to be close to spherical with particles in size range 17–19 nm by TEM. Another part of microwave precursor on calcination at 1000 °C for 3 h led to formation of fully crystalline Nd:Y₂O₃ with particles in size range of 35–85 nm. Both partially crystalline amorphous precursor and fully crystalline Nd:Y₂O₃ were compacted at 400 MPa by cold isostatic press and sintered at 1750 °C for 10 h under vacuum (10^?5 mbar). The partially crystalline Nd:Y₂O₃ amorphous precursor densified to 99% with 65% transmission at 2500 nm (0.5 mm thickness) compared to 96% densification with 34% transmission for fully crystalline Nd:Y₂O₃ without any sintering aids. Retention of cubic phase purity of Y₂O₃ was observed in both the ceramic pellets post sintering by XRD. Good grain fusion with grain growth to ≤2 μm was observed by scanning electron microscope (SEM) for partially crystalline Nd:Y₂O₃ amorphous precursor. Thus partially crystalline Nd:Y₂O₃ amorphous precursor nanopowders, with homogeneous close to spherical fine particles and high reactivity due to ionic mobility of amorphous phase, led to better densification.     

Nano-Y2O3-coated LiNi0.5Co0.2Mn0.3O2 cathodes with enhanced electrochemical stability under high cut-off voltage and high temperature

LiNi_0.5Co_0.2Mn_0.3O₂ (523) coated with ~ 20 nm thick Y₂O₃ nano-membrane is prepared via a sol-type chemical precipitation process based on electrostatic attraction between the materials. The nano-Y₂O₃-coated 523 cathode can deliver 160.3 mA h g⁻¹ (87.8% of its initial discharge capacity) after 50 cycles at 1 C (180 mA g⁻¹) between 3.0 and 4.6 V by coin cell testing, while the pristine 523 keeps only 146.2 mA h g⁻¹ with 78.6% capacity retention left. The capacity retention rate increases from 50% to 86.7% after 150 cycles at 1 C in 3.0–4.35 V by soft package testing under 45 °C. Through this novel Y₂O₃ coating operation, both the charge transfer resistance and the electrode polarization of the 523 electrode have been suppressed, and its structure stability is also improved.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Y(PO4)3 red phosphors

A series of red-emitting phosphors Eu³⁺-doped Sr₃Y(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Y(PO₄)₃:Eu³⁺ phosphors exhibit peaks associated with the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The integral intensity of the emission spectra of Sr₃Y_0.94(PO₄)₃:0.06Eu³⁺ phosphors excited at 392 nm is about 3.4 times higher than that of Y₂O₃:Eu³⁺ commercial red phosphor. The Commission Internationale de l’Eclairage chromaticity coordinates, the quantum efficiencies and decay times of the phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Y(PO₄)₃ phosphors are promising red-emitting phosphors pumped by near-UV light.     

White luminescence of bismuth and samarium codoped Y2O3 phosphors

In this work Sm³⁺ (0–2.0 at%) and Bi³⁺ (0–2.0 at%) doped Y₂O₃ luminescent powders were prepared by a sol–gel method from yttrium acetylacetonate, samarium and bismuth nitrates as metal sources. The as prepared powders (chemical composition is close to stoichiometric Y₂O₃) present the cubic structure from 700 °C, and at 900 °C are characterized by the presence of rounded particles with heterogeneous size of 42.9 nm. Luminescent effect of ions of Sm³⁺ and Bi³⁺ into Y₂O₃ host as was studied on heat treated powders from 800 to 1100 °C. The combination of the red luminescence from the Sm³⁺ ions and the bluish from Bi³⁺, makes the synthesized phosphors candidates to be used in fabrication of phosphor-converted light-emitting diodes (LEDs).     

Gel-combustion assisted synthesis of eulytite-type Sr3Y(PO4)3 as a single host for narrow-band Eu3+ and broad-band Eu2+ emissions

A series of eulytite-type Sr₃Y_1-x(PO₄)₃:xEu³⁺ (x = 0–0.13) and Sr_3-yY(PO₄)₃:yEu²⁺ (y = 0–0.10) phosphors were successfully synthesized via gel-combustion and subsequent calcination in O₂ and Ar/H₂ atmospheres at 1250 °C, respectively. Detailed crystal structure analysis via Rietveld refinement showed that the phosphors were crystallized in the cubic system (space group I-43d, No. 220), in which the Eu³⁺ and Eu²⁺ activators reside at the Y³⁺ and Sr²⁺ sites, respectively. The trivalent Eu³⁺ ions (CN = 6) exhibited typical narrow-band luminescence via intra-4f⁶ transitions, with the red emission at ~ 615 nm being dominant (⁵D₀ → ⁷F₂ transition, FWHM = 15.9 ± 0.2 nm). The divalent Eu²⁺ ions (CN = 6 and 9) showed broad-band luminescence ranging from light-blue to blue via 4f⁶5d¹ → 4f⁷ transitions (FWHM = 115 ± 2 nm). The optimal Eu³⁺ and Eu²⁺ concentrations were determined to be 10 at% (x = 0.10) and 7 at% (y = 0.07), respectively, and the mechanisms of concentration quenching were discussed. The excitation/emission properties, fluorescence decay kinetics, CIE chromaticity, and particularly the rarely addressed thermal stability of the phosphors were investigated in detail.     

Synthesis and characterization of the crystalline powders on the basis of Lu2O3:Eu3+spherical submicron-sized particles

This study is devoted to the preparation of the crystalline powders on the basis of non-agglomerated monodisperse Lu₂O₃:Eu³⁺ spherical particles with the diameters in the range of 50–250 nm by the soft chemistry co-precipitation route. The influence of the synthesis parameters on control morphology, particles size and agglomeration in the final Lu₂O₃:Eu³⁺ powder was considered. Lu₂O₃:Eu³⁺ crystalline powders were characterized by means of electron microscopy methods (TEM, SEM), FT-IR spectroscopy, thermal analysis (TG-DTA) and X-ray diffractometry. The mechanisms of the precursor decomposition and crystallization at the temperatures ranging from 60 to 900 °C were discussed. It was shown that the powders obtained were characterized by the effective luminescence under X-ray excitation in λ = 575–725 nm spectral region corresponding to ⁵D₀ → ⁷F_J transitions (J = 0–4) of Eu³⁺ ions with a maximum at 612 nm and the luminescence intensity strongly depends on annealing temperature. The relative densities of the green-bodies on the basis of Lu₂O₃:Eu³⁺ powders were estimated and the sintering of compacts at the temperatures up to 1500 °C was studied.     

Spark plasma sintering of transparent Y2O3 ceramic using hydrothermal synthesized nanopowders

Y₂O₃ nanopowders were synthesized by the hydrothermal treatment of Y(NO₃)₃·6H₂O and citric acid (CA) as Y⁺³ and the capping agent, respectively. The effect of different CA:Y⁺³ mol ratios, heat treatment time, and calcination temperature was investigated in order to determine their influence on the morphology, particle size and phase of Y₂O₃ nanopowders. The narrow size distribution of particles was obtained with CA:Y⁺³ mol ratio=1.6, heat treatment time of 6 h, and a calcination temperature at 900 °C for 90 min. Then, the synthesized Y₂O₃ nanopowder was consolidated by the spark plasma sintering technique at 1500 °C with a heating rate of 100 °C/min and held for 8 min before turning off the power. As a result, the ceramic prepared with 3 mm thickness got the highest transmission of 80% at 2.5–6 µm wavelength. The highest density and the grain size of yttria ceramic were 99.58% and 1–1.2 µm at 1500 °C, respectively.     

Electric field enhancements in In2O3-coated single-walled carbon nanotubes

In₂O₃ nanoparticles are coated on the surfaces of single-walled carbon nanotubes (SWCNTs) by a successive ionic layer adsorption and reaction process. The thickness of the In₂O₃ nanoparticle film is tuned by controlling the number of coating cycles. The electric field around the In₂O₃-coated SWCNTs is compared with that of pristine SWCNTs. Field enhancement of the In₂O₃-coated SWCNTs is confirmed by conductive atomic force microscopy at low electric field (contact mode: 1 V to −1 V) and also field emission (FE) analysis at high electric field (0–4.2 V/μm). The uniformity and emission stability are also measured via FE analysis. Near infrared and X-ray photoemission spectroscopy data are suggested to explain the charge transfer, bandgap change between the In₂O₃ nanoparticles and SWCNTs, and the electric field enhancements in the In₂O₃-coated SWCNTs at both low and high electric field.     

Fabrication of Lu2O3:Eu transparent ceramics using powder consisting of mono-dispersed spheres

Mono-dispersed spherical Lu₂O₃:Eu (5 mol%) powders for transparent ceramics fabrication were synthesized by urea-based homogeneous precipitation technique. The effects of the doped-Eu³⁺ on the synthesis of Lu₂O₃:Eu particles were investigated in detail. The results show that the doping of Eu³⁺ ions into Lu system can significantly decrease the particle size of the resultant precursor spheres. Owing to the sequential precipitation in Lu/Eu system, there are compositional gradients within each of the resultant precursor spheres. Well dispersed, homogeneous and spherical/near spherical Lu₂O₃:Eu powders were obtained after calcination at 600–1000 °C for 4 h. The powder calcined at 600 °C shows better sintering behavior and can be densified into transparent ceramic after vacuum sintering at 1700 °C for 5 h. The luminescence properties of the obtained Lu₂O₃:Eu powder and transparent ceramic were also studied.     

ZrO2-doped Y2O3 transparent ceramics via slip casting and vacuum sintering

Commercial Y₂O₃ powder was used to fabricate highly transparent Y₂O₃ ceramics with the addition of ZrO₂ via slip casting and vacuum sintering. The effects of ZrO₂ addition on the transparency, grain size and lattice parameter of Y₂O₃ ceramics were studied. With addition of ZrO₂ the transparency of Y₂O₃ ceramics increased markedly and the grain size of Y₂O₃ ceramics decreased markedly by cation diffusivity mechanism and the lattice parameter of Y₂O₃ ceramics slightly decreased. The highest transmittance (at wavelength 1100 nm) of the 5.0 mol% ZrO₂–Y₂O₃ ceramic (1.0 mm thick) sintered at 1860 °C for 8 h reached 81.7%, very close to the theoretical value of Y₂O₃.     

Effects of Eu content on the luminescent properties of Y2O3:Eu3+ aerogels and Y(OH)3/Y2O3:Eu3+@SiO2 glassy aerogels

This article describes the morphological, structural, and luminescent properties of Y₂O₃:Eu³⁺ aerogels and Y(OH)₃/Y₂O₃:Eu³⁺@SiO₂ glassy aerogels synthesized by the sol-gel method with Eu concentrations from 2.5 mol% to 30 mol%. XRD measurements indicated that both the aerogels and glassy aerogels had a monoclinic phase, but the crystallinity in the glassy aerogels was lower due to the presence of SiO₂. SEM images reveal that a three-dimensional porous network was formed in the aerogels due to the interconnection of coalesced Y₂O₃:Eu³⁺ nanoparticles. The 3D porous network was also observed in the glassy aerogels, coated with a silica shell. In both the aerogels and glassy aerogels, the size of the agglomerates decreased as the europium concentration increased. This, in turn, increased the average size of the macropores that formed their 3D network. Furthermore, the luminescent properties of the aerogels and glassy aerogels were studied under UV excitation, and it was observed that their red emission intensity increased continuously as the Eu³⁺ concentration increased. The luminescence of the aerogels was on average 50% higher than that of the glassy aerogels. Hence, our results indicate that porous and luminescent aerogels with and without silica are adequate for applications in sensing and catalysis.     

Sintering of Yb3+:Y2O3 transparent ceramics in hydrogen atmosphere

Highly transparent Yb³⁺:Y₂O₃ ceramics with doping concentration up to 40.0 at.% had been fabricated successfully via hydrogen atmosphere sintering, where the raw powders were synthesized by co-precipitation method. The sintering temperature is about 600 °C lower than its melting temperature. SEM investigation revealed the average grain size of Yb³⁺:Y₂O₃ ceramics sintered at 1850 °C for 9 h was about 7 μm. The highest transmittance of as-prepared 1 mm thickness samples around wavelength of 1050 nm reached 80%, which is close to the theoretical value of Y₂O₃. The optical spectroscopic properties of Yb³⁺:Y₂O₃ transparent ceramics have also been investigated, which shows that it is a very good laser material for diode laser pumping and short pulse mode-locked laser.     

Influence of deposition temperature on luminescent efficiency of Y2O3:Eu3+ thin films deposited on quartz fabric by EBE

Y₂O₃:Eu³⁺ thin films were grown on quartz fabric substrate by electron beam evaporation (EBE) at different deposition temperatures. It was found that an increase of deposition temperature from room temperature (R.T.) to 250 °C results in improved morphologies of the films, such as reduced defects, spherical particle shape and dense surface topography. A change in the predominant orientation of Y₂O₃:Eu³⁺ thin films was detected from (222) at low temperatures of R.T.–150 °C to (400) at higher temperatures of 200–250 °C. The luminescent intensity of the films was gradually improved with an increase in deposition temperature and the optimal brightness was observed when the films were grown at 250 °C and improved by 32.67% in comparison with that of the films grown at R.T. The results reveal that the improved morphologies and effective crystallization can contribute to the enhanced luminescent properties of the Y₂O₃:Eu³⁺ thin films.     

Effects of ZrO2-La2O3 co-addition on the microstructural and optical properties of transparent Y2O3 ceramics

Commercial Y₂O₃ powder was used to fabricate Y₂O₃ ceramics sintered at 1600 °C and 1800 °C with concurrent addition of ZrO₂ and La₂O₃ as sintering aids. One group with different contents of La₂O₃ (0–10 mol%) with a fixed amount of 1 mol% ZrO₂ and another group with various contents of ZrO₂ (0–7 mol%) with a fixed amount of 10 mol% La₂O₃ were compared to investigate the effects of co-doping on the microstructural and optical properties of Y₂O₃ ceramics. At low sintering temperature of 1600 °C, the sample single doped with 10 mol% La₂O₃ exhibits much denser microstructure with a few small intragranular pores while the samples with ZrO₂ and La₂O₃ co-doping features a lot of large intergranular pores leading to lower density. When the sintering temperature increases to 1800 °C, samples using composite sintering aids exhibit finer microstructures and better optical properties than those of both ZrO₂ and La₂O₃ single-doped samples. It was proved that the grain growth suppression caused by ZrO₂ overwhelms the acceleration by La₂O₃. Meanwhile, 1 mol% ZrO₂ acts as a very important inflection point with regard to the influence of additive concentration on the transmittance, pore structure and grain size. The highest in-line transmittance of Y₂O₃ ceramic (1.2 mm in thickness) with 3 mol% of ZrO₂ and 10 mol% of La₂O₃ sintered at 1800 °C for 16 h is 81.9% at a wavelength of 1100 nm, with an average grain size of 11.2 µm.     

CeF3-modified LiNi1/3Co1/3Mn1/3O2 cathode material for high-voltage Li-ion batteries

A facile chemical deposition method has been adopted to prepare cerium fluoride (CeF₃) surface modified LiNi_1/3Co_1/3Mn_1/3O₂ as cathode material for lithium-ion batteries. Structure analyses reveal that the surface of LiNi_1/3Co_1/3Mn_1/3O₂ particles is uniformly coated by CeF₃. Electrochemical tests indicate that the optimal CeF₃ content is 1 wt%. The 1 wt% CeF₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ can deliver a discharge capacity of 107.1 mA h g⁻¹ even at 5 C rate, while the pristine does only 57.3 mA h g⁻¹. Compared to the pristine, the 1 wt% CeF₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ exhibits the greatly enhanced capacity and cycling stability in the voltage range of 3.0–4.5 V, which suggests that the CeF₃ coating has the positive effect on the high-voltage application of LiNi_1/3Co_1/3Mn_1/3O₂. According to the analyses from electrochemical impedance spectra, enhanced electrochemical performance is mainly because the stable CeF₃ coating layer can prevent the HF-containing electrolyte from continuously attacking the LiNi_1/3Co_1/3Mn_1/3O₂ cathode and retard the passivating layer growth on the cathode.     

Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Tunable white light and energy transfer of Dy3+ and Eu3+ doped Y2Mo4O15 phosphors

A series of Dy³⁺ or/and Eu³⁺ doped Y₂Mo₄O₁₅ phosphors were successfully synthesized at a low temperature of 600 °C via solid state reaction. The as-prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electronic microscope (SEM), photoluminescence (PL) excitation, emission spectra and PL decay curves. XRD results demonstrate that Y₂Mo₄O₁₅: Dy³⁺, Eu³⁺ has the monoclinic structure with the space group of p21/C(14). Under the excitation of ultraviolet (UV) or near-UV light, the Dy³⁺ and Eu³⁺ ions activated Y₂Mo₄O₁₅ phosphors exhibit their characteristic emissions in the blue, yellow and red regions. The emitting light color of the Y₂Mo₄O₁₅: 0.08Dy³⁺, yEu³⁺ phosphors can be adjusted by varying the concentration ratio of Dy³⁺ to Eu³⁺ ions and a white light is achieved when the doping concentration of Eu³⁺ is 5%. In addition, the energy transfer from Dy³⁺ to Eu³⁺ is also confirmed based on the luminescence spectra and decay curves.