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.     

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.     

Color-tunable up-conversion emission from Yb3+/Er3+/Tm3+/Ho3+ codoped KY(MoO4)2 microcrystals based on energy transfer

Tunable up-conversion luminescent material KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) has been synthesized by a typical hydrothermal process. Under 980 nm laser diode (LD) excitation, the emission intensity and the corresponding luminescence colors of KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) have been investigated in detail. The energy transfer from the Yb³⁺ sensitizer to Ho³⁺, Er³⁺ and Tm³⁺ activators plays an important role in the development of color-tunable single- phased phosphors. The emission intensity keep balance through control of the Ho³⁺ co-doping concentrations, white light was experimentally shown at KY(MoO₄)₂: 20 mol% Yb³⁺, 0.8 mol% Er³⁺, 0.5 mol% Tm³⁺, 1.0 mol% Ho³⁺ phosphor with further calcination at 800 °C for 4 h under 980 nm laser excitation. The color tunability, high quality of white light and high intensity of the emitted signal make these up-conversion (UC) phosphors excellent candidates for applications in solid-state lighting.     

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).     

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.     

Microwave-assisted polyol synthesis of sub-micrometer Y2O3 and Yb-Y2O3 particles for laser source application

Sub-micrometer powder (100–150 nm diameter) of Yb-doped yttrium oxide was obtained, for the first time, by microwave-assisted polyol (diethylene glycol, DEG) method. This method is based on fast and homogeneous increase of temperature, due to the microwave heating, and on addition of the hydrolysing agent (water) at high temperature. This promotes a fast nucleation followed by a controlled growth of nuclei. Different procedures were used to process the as-synthesized powders. In some cases washing by ultrapure water was used to dissolve nitrate and DEG by-products, this treatment allowed the use of a lower calcination temperature (150–200 °C less) to obtain the crystalline phase. Analysis of the calcined powder showed different levels of structures: from nanocrystal (10–15 nm), to primary particles (100–150 nm), to micrometer soft aggregates (2–4 μm). The microwave-assisted polyol method resulted an easy way to dope yttria with the desired amount of Yb³⁺. This work was carried out in order to prepare particles to be used as rare-earth doped Y₂O₃ and YAG polycrystalline transparent ceramic for laser source applications.     

Preparation and infrared to visible upconversion luminescence of Yb2O3:Ho3+ nanocrystalline powders

Yb₂O₃:Ho³⁺ nanocrystalline powders were synthesized through a solid state reaction method. X-ray diffraction analysis and field emission scanning electron microscopy were used to analyze the phase composition and morphology of the powders. Then under the 980 nm excitation of laser diode, the fluorescence of the crystals was studied via a fluorescence spectrometer. The green and red emissions centered on 551 and 668 nm were observed, and the green band dominated the emission spectrum. The effect of the concentration of Ho³⁺ on the upconversion luminescence intensity was discussed and the possible upconversion emission mechanism was explained. It indicates that like other metal oxide nanoparticles, Yb₂O₃ could also be a potential host material for doping to prepare the upconversion phosphor.     

Densification of nanocrystalline Y2O3 ceramic powder by spark plasma sintering

Nanocrystalline Y₂O₃ powders with 18 nm crystallite size were sintered using spark plasma sintering (SPS) at different conditions between 1100 and 1600 °C. Dense specimens were fabricated at 100 MPa and 1400 °C for 5 min duration. A maximum in density was observed at 1400 °C. The grain size continuously increased with the SPS temperature into the micrometer size range. The maximum in density arises from competition between densification and grain growth. Retarded densification above 1400 °C is associated with enhanced grain growth that resulted in residual pores within the grains. Analysis of the grain growth kinetics resulted in activation energy of 150 kJ mol^?1 and associated diffusion coefficients higher by 10³ than expected for Y³⁺ grain boundary diffusion. The enhanced diffusion may be explained by combined surface diffusion and particle coarsening during the heating up with grain boundary diffusion at the SPS temperature.     

Yb3+ concentration on emission color,thermal sensing and optical heater behavior of Er3+ doped Y6O5F8 phosphor

Up-conversion phosphor is a potential candidate as non-contact temperature sensor because of its unjammable and unique detection abilities. In this work, we investigate the influence of Yb³⁺ concentration on the emission color, thermal sensing and optical heater behavior of Er³⁺ doped Y₆O₅F₈ phosphor. Our results show that the emission color of Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder changes from green to yellow with the Yb³⁺ concentration increasing. Importantly, the temperature sensing sensitivities of Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder reach 0.008, 0.009, 0.010 and 0.011 K⁻¹ as the sample doped with 2%, 5%, 8% and 11% Yb³⁺ at 476 K, respectively. Moreover, the temperature of high Yb³⁺ concentration sample shows preferable optical heating behavior, whose temperature is ascended by a large value of 94 K when the excitation pump power density changes from 1.0 to 13.1 W cm⁻². These results suggest Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder has great potential in colorful display, temperature sensing and optical heating.     

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.     

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.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

Up-conversion emission color tuning in NaLa(MoO4)2: Nd3+/Yb3+/Ho3+ excited at 808 nm

As alternatives to Yb³⁺-sensitized up-conversion (UC) materials excited at 980 nm, Nd³⁺-sensitized UC phosphors irradiated by 808 nm have been used to decrease the absorption of water and alleviate the overheating effect in vivo biological application. Intense red and green UC emissions from ⁵F₅→⁵I₈ and ⁵F₄/⁵S₂→⁵I₈ transitions of Ho³⁺ appeared in Nd³⁺/Yb³⁺/Ho³⁺ tri-doped NaLa(MoO₄)₂ through successive energy transfer Nd³⁺→Yb³⁺→Ho³⁺ under 808 nm excitation, in which Yb³⁺ ions were proven to be the energy transfer bridge between Nd³⁺ and Ho³⁺ by lifetime measurement. The variable emission color and intensity ratios of red to green emissions were realized by adjusting the doping concentration of Yb³⁺, pulse width of the excitation laser and the addition of Ce³⁺ ion, which depends on the different population pathways to the green and red emitting states of Ho³⁺. The chromaticity modulation mechanisms of these approaches were proposed, which provides a feasible strategy to tune the UC emission color.     

Mechanical and optical properties of spark plasma sintered transparent Y2O3 ceramics

Commercial Y₂O₃ nanopowder was used to fabricate transparent Y₂O₃ ceramics by spark plasma sintering under the pressure of 100 MPa for 20 min with the heating rate of 100 °C/min. The microstructures, mechanical and optical properties of the Y₂O₃ ceramics sintered at different temperatures were investigated in detail. Densification occurred up to a sintering temperature of 1500 °C, and above 1500 °C, rapid grain growth and pore growth occurred. The highest relative density of 99.58% and the minimum average grain size of 0.58±0.11 µm were obtained at 1500 °C. The flexural strength, hardness and fracture toughness of the optimal spark plasma sintered Y₂O₃ ceramic were 122 MPa, 7.60 GPa and 2.06 MPa.m^1/2, respectively. The Y₂O₃ ceramic sintered at 1500 °C had the in-line transmission of about 11–54% and 80% in the wavelength range of 400–800 nm and 3–5 µm, respectively.     

Up-conversion luminescence and optical thermometry properties of transparent glass ceramics containing CaF2:Yb3+/Er3+ nanocrystals

A series of Yb³⁺/Er³⁺ codoped transparent oxyfluoride glass ceramics with various amounts of Yb³⁺ have been successfully fabricated and characterized. Under 980 nm laser prompting, the samples produce intense red, green and blue up-conversion emissions, and the emission intensities increase with Yb³⁺ concentration and heat treatment temperature. Before losing good transparency in the visible region, optimum emission intensities are obtained for the sample with 25 mol% of Yb³⁺ at a heat treatment temperature of 680 °C. A possible up-conversion mechanism is proposed from the dependence of emission intensities on pumping power. The fluorescence intensity ratio between the two thermally coupled levels ²H_11/2 versus ⁴S_3/2 was measured with the laser output power of 57 mW to avoid the possible laser induced heating effect. The fluorescence intensity ratio values in the temperature range from 295 K to 723 K can be well fitted with the equation: A exp (−∆E/k_BT), where A = 6.79 and ∆E=876 cm⁻¹. The relative temperature sensitivity at 300 K was evaluated to be 1.4% K⁻¹. All the results suggest that the Yb³⁺/Er³⁺ codoped CaF₂ glass ceramics is an efficient up-conversion material with potential in optical fiber temperature sensing.     

Influence of Yb3+ doping on phase stability and thermophysical properties of (Y1-xYbx)3Al5O12 under high temperature

In this work, Yb³⁺ was selected to replace the Y³⁺ in yttrium aluminum garnet (YAG) in order to reduce its thermal conductivity under high temperature. A series of (Y_1-xYb_x)₃Al₅O₁₂ (x=0, 0.1, 0.2, 0.3, 0.4) ceramics were prepared by solid-state reaction at 1600 °C for 10 h. The microstructure, thermophysical properties and phase stability under high temperature were investigated. The results showed that all the Yb doped (Y_1-xYb_x)₃Al₅O₁₂ ceramics were comprised of a single garnet-type Y₃Al₅O₁₂ phase. The thermal conductivities of (Y_1-xYb_x)₃Al₅O₁₂ ceramics firstly decreased and subsequently increased with Yb ions concentration rising from room temperature to 1200 °C. (Y_0.7Yb_0.3)₃Al₅O₁₂ had the lowest thermal conductivity among investigated specimens, which was about 1.62 W m⁻¹ K⁻¹ at 1000 °C, around 30% lower than that of pure YAG (2.3 W m⁻¹ K⁻¹, 1000 °C). Yb had almost no effect on the coefficients of thermal expansion (CTEs) of (Y_1-xYb_x)₃Al₅O₁₂ ceramics and the CTE was approximate 10.7×10⁻⁶ K⁻¹ at 1200 °C. In addition, (Y_0.7Yb_0.3)₃Al₅O₁₂ ceramic remained good phase stability when heating from room temperature to 1450 °C.     

Upconverting luminescence based dual-modal temperature sensing for Yb3+/Er3+/Tm3+: YF3 nanocrystals embedded glass ceramic

Yb³⁺/Er³⁺/Tm³⁺ doped transparent glass ceramic containing orthorhombic YF₃ nanoparticles was successfully synthesized by a melt-quenching method. After glass crystallization, tremendously enhanced (about 5000 times) upconversion luminescence, obvious Start-splitting of emission bands as well as long upconversion lifetimes of Er³⁺/Tm³⁺ confirmed the incorporation of lanthanide activators into precipitated YF₃ crystalline environment with low phonon energy. Furthermore, temperature-dependent upconversion luminescence behaviors of glass ceramic were systematically investigated to explore its possible application as optical thermometric medium. Impressively, both fluorescence intensity ratio of Er³⁺: ²H_11/2 → ⁴I_15/2 transition to Er³⁺: ⁴S_3/2 → ⁴I_15/2 one and fluorescence intensity ratio of Tm³⁺: ³F_2,3 → ³H₆ transition to the combined Tm³⁺: ¹G₄ → ³F₄/Er³⁺: ⁴F_9/2 → ⁴I_15/2 ones were demonstrated to be applicable as temperature probes, enabling dual-modal temperature sensing. Finally, the thermal effect induced by the irradiation of 980 nm laser was found to be negligible in the glass ceramic sample, being beneficial to gain intense and precise probing signal and detect temperature accurately.     

Phase stability and thermal conductivity of RE2O3 (RE=La,Nd, Gd,Yb) and Yb2O3 co-doped Y2O3 stabilized ZrO2 ceramics

Y₂O₃ stabilized ZrO₂ (YSZ) has been considered as the material of choice for thermal barrier coatings (TBCs), but it becomes unstable at high temperatures and its thermal conductivity needs to be further reduced. In this study, 1 mol% RE₂O₃ (RE=La, Nd, Gd, Yb) and 1 mol% Yb₂O₃ co-doped YSZ (1RE1Yb–YSZ) were fabricated to obtain improved phase stability and reduced thermal conductivity. For 1RE1Yb–YSZ ceramics, the phase stability of metastable tetragonal (t′) phase increased with decreasing RE³⁺ size, mainly attributable to the reduced driving force for t′ phase partitioning. The thermal conductivity of 1RE1Yb–YSZ was lower than that of YSZ, with the value decreasing with the increase of the RE³⁺ size mainly due to the increased elastic field in the lattice, but 1La1Yb–YSZ exhibited undesirably high thermal conductivity. By considering the comprehensive properties, 1Gd1Yb–YSZ ceramic could be a good potential material for TBC applications.     

Concentration effects on the upconversion luminescence in Ho3+/Yb3+ co-doped NaGdTiO4 phosphor

Ho³⁺/Yb³⁺ co-doped NaGdTiO₄ phosphors were synthesized by a solid-state reaction method. The upconversion (UC) luminescence characteristics excited by 980 nm laser diode were systematically investigated. Bright green UC emission centered at 551 nm accompanied with weak red and near infrared (NIR) UC emissions centered at 652 and 761 nm were observed. The dependence of UC emission intensity on excitation power density showed that all of green, red and NIR UC emissions are involved in two-photon process. The UC emission mechanisms were discussed in detail. Concentration dependence studies indicated that Ho³⁺ and Yb³⁺ concentrations had significant influences on UC luminescence intensity and the intensity ratio of the red UC emission to that of the green one. Rate equations were established based on the possible UC mechanisms and a theoretical formula was proposed to describe the concentration dependent UC emission. The UC luminescence properties of the presented material was evaluated by comparing with commercial NaYF₄:Er³⁺, Yb³⁺ phosphor, and our sample showed a high luminescence efficiency and good color performance, implying potential applications in a variety of fields.     

Ionic conductivity and mechanical properties of Y2O3-doped CeO2 ceramics synthesis by microwave-induced combustion

We developed a new method, i.e. microwave-induced combustion synthesis to produce highly sinterable Y₂O₃-doped CeO₂ nanopowders. The process took only 15 min to yield Y₂O₃-doped CeO₂ powders. We also investigated the conductivity of Y₂O₃-doped CeO₂ ceramics. It was found Y₂O₃ concentration to have a large effect on the morphology, activation energy, ionic conductivity, and mechanical properties of Y₂O₃-doped CeO₂ ceramics. The results revealed that the bulk densities of Y₂O₃-doped CeO₂ ceramics sintered at 1420 °C for 5 h were all higher than 92% of the theoretical densities, and the maximum ionic conductivity, σ_800 °C = 0.023 S/cm at 800 °C, the minimum activation energy, E_a = 0.954 eV determined in the temperature of 300–800 °C and the maximum fracture toughness, K_IC = 1.825 ± 0.188 MPa m^1/2 were found for 9 mol.% Y₂O₃-doped CeO₂ specimen. The grain size of CeO₂ decreases with increasing Y₂O₃ concentration. The fracture toughness was found to increase at increased Y₂O₃ concentration, because of the decrease of CeO₂ grain size.