X-ray Diffraction and 151Eu Mössbauer Spectroscopic Study of the Hf1−xEuxO2−x/2(0 ≤x≤ 1.0) System

Powder X-ray diffractometry (XRD) and ¹⁵¹Eu Mössbauer spectroscopy were performed for samples prepared in the temperature range 1500–1500°C for the hafnia–europia (HfO₂–Eu₂O₃) system Eu _x Hf_{1− x} O_{2− x /2}(0 ≤ x ≤ 1.0). The XRD results showed that two types of solid solution phases formed in the composition range 0.25 ≤ x ≤ 0.725: an ordered pyrochlore-type phase in the middle-composition range (0.45 < x < 0.575) and a disordered fluorite-type phase, enveloping the pyrochlore-type phase on both sides, in the composition ranges 0.25 ≤ x ≤ 0.40 and 0.60 ≤ x ≤ 0.725. ¹⁵¹Eu Mössbauer spectroscopy sensitively probes local environmental changes around trivalent europium (Eu³⁺) caused by the formation of these solid solution phases. In addition to the broad, single Mössbauer spectra observed in this study for the Eu³⁺, the values of isomer shift (IS) exhibited a pronounced minimum in the neighborhood of the stoichiometric pyrochlore phase ( x ≈ 0.5). Such IS behavior of Eu³⁺ was interpreted based on the XRD crystallographic information that the ordered pyrochlore phase has a longer (in fact, the longest) average Eu–O bond length than those of the disordered fluorite phases on both sides or the monoclinic (and C-type) Eu₂O₃at x = 1.0.     

Structural and Photoluminescence Properties of Ce3+- and Tb3+-Activated Lu-α-Sialon

The crystal structure and photoluminescence properties of undoped and Ce³⁺- or Tb³⁺-doped Lu-α-Sialon are reported. Lu-α-Sialon with the composition of Lu_0.367Si_9.9Al_2.1ON₁₅ crystallizes in a trigonal system with a =7.8013(1) Å, c =5.6827(1) Å, in the space group P 31 c . The Lu³⁺ ion is accommodated at the interstice site at 2 b and directly connected by seven (N, O) atoms with an average bond length of 2.624 Å. The incorporation of large Ce³⁺ and Tb³⁺ ions on small Lu³⁺ site results in the expansion of the unit cell as expected but keeping the average Lu_Ln-(N, O) (Ln=Ce, Tb) distances nearly constant with slight distortion in the lattices. The optical band gap of Lu-α-Sialon is about 5.25 eV determined by the diffused reflection spectrum. Lu-α-Sialon:Ce³⁺ (2 mol%) exhibits efficiently greenish-blue emission at about 486 nm under near-ultraviolet (UV) excitation originating from the 5 d →4 f ¹5 d ⁰ transition of Ce³⁺. Lu-α-Sialon:Ce³⁺ is a potential candidate phosphor for white UV-LED applications due to its high quantum efficiency and excellent thermal stability. Lu-α-Sialon:Tb³⁺ (2 mol%) emits strong mixed blue and green light in equivalent due to the transitions of ⁵D₃→⁷F_J and ⁵D₄→⁷F_J of Tb³⁺.     

Duplex α,β-Sialon Ceramics Stabilized by Dysprosium and Samarium

Duplex αβ,-sialon ceramics with a minimum volume fraction of residual intergranular glass have been prepared using Dy or Sm as the α-sialon stabilizing element. These microstructures contained high aspect ratio β-sialon grains homogeneously distributed in an α-sialon matrix. A number of the larger α-sialon grains contained dislocations and showed a core/shell structure. Dy gave an α-sialon which was stable over a wide temperature range (1350–1800°C) for long holding times, while the use of Sm resulted in less stable α-sialon structures at medium temperatures (1450°C) and the formation of melilite, R₂Si_3−xAl_xO_3+xN_4−x, β-sialon, and the 21R sialon polytype during prolonged heating. High α-phase contents gave a very high hardness ( H _V10 is approximately 22 GPa) but a comparatively low indentation fracture toughness (around 4.4 MPam^1/2). Duplex sialons fabricated from powder mixtures corresponding to an α-to-β sialon ratio of around 50:50 resulted in a sialon material with a favorable combination of high hardness (around 22 GPa) and increased toughness (to around 5.5 MPam^1/2).     

Photoluminescence of Rare-Earth-Doped Ca-α-SiAlON Phosphors: Composition and Concentration Dependence

Rare-earth-doped Ca-α-SiAlON phosphors, with the compositions of (Ca_{1−3/2 x} RE _x ) _{m /2}Si_{12− m − n} Al _m+n O _n N_{16− n} (RE=Ce, Sm, and Dy, 0.5≤ m =2 n ≤3.0), were prepared by sintering at 1700°C for 2 h under 10 atm N₂. The concentration of rare earths varied from 3 to 30 at.% with respect to Ca. The photoluminescence (PL) properties were investigated as functions of the composition of the host matrix (i.e., m ) and the concentration of rare earths (i.e., x ). The results show that the emission properties can be optimized by tailoring m and x . The Ce³⁺ luminescence originating from the 4 f –5 d interconfigurational transitions is greatly affected by the environment surrounding the Ce³⁺ ions, which differs from the Sm³⁺ or Dy³⁺ luminescence arising from the 4 f –4 f intraconfigurational transitions. X-ray diffraction and scanning electron microscopy were used to explain the composition and concentration dependence of PL properties.     

Characterization of Ca2SiO4:Eu2+ Phosphors Synthesized by Polymeric Precursor Process

The green emitting Ca₂SiO₄:Eu²⁺ (C₂S:Eu) phosphors were synthesized by the polymeric precursor process (Pechini-type), and the effects of calcination temperature and europium (Eu) doping concentration on the luminescent properties were investigated. The crystalline β-C₂S was obtained in the calcination temperature of 1100°–1400°C, and Eu was reduced into Eu²⁺ by annealing in 5% H₂/N₂ atmosphere. The obtained C₂S:Eu²⁺ phosphors exhibited a strong emission at 504 nm under the excitation of λ_exc=350 nm. The highest photoluminescence (PL) intensity was observed in the C₂S:Eu²⁺ phosphors either calcined at 1300°C or doped with 3 mol% Eu. The obtained PL properties were discussed in terms of crystal structure, particle size and shape, surface roughness, and effect of concentration quenching.     

Synthesis and Photoluminescence of Eu2+-Doped α-Silicon Nitride Nanowires Coated with Thin BN Film

A feasible doping strategy is introduced to synthesize Eu²⁺-doped α-Si₃N₄ nanowires coated with a thin BN film. The nanowires were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, and a fluorescence spectrophotometer. The Eu²⁺-doped α-Si₃N₄ nanowires emitted strong yellow light, which is related to the 4 f ⁶5 d –4 f ⁷ transition of Eu²⁺, upon a broad excitation wavelength range between 250 and 450 nm. The obtained nanowires provided a potential candidate for application in optical nanodevices, as well as in white LEDs.     

Ca2B5O9Cl:Eu2+, A Suitable Blue-Emitting Phosphor for n-UV Excited Solid-State Lighting

Blue-emitting Ca₂B₅O₉Cl:Eu²⁺ phosphors have been synthesized by solid state reaction. The photoluminescence excitation (PLE) spectra show broad-band absorptions and can match the emission of near ultraviolet (n-UV) chip well. At lower Eu²⁺ concentration, the emission band can be resolved into two bands, which is assigned to the 5 d →4 f transition of Eu²⁺ ions substituting two different Ca²⁺ sites. At higher Eu²⁺ concentration, the energy transfer from Eu(1) to Eu(2) happens and is very efficient. At higher temperature the phosphor exhibits a lower temperature quenching effect. The fluorescence lifetimes are short enough for application in solid-state lighting. The electroluminescence spectrum indicates that the emission of chip can almost be absorbed by phosphor and down-converted into an intensive blue light. The chromaticity coordinates of fabricated light-emitting-diodes (LEDs) is very close to that of BaMgAl₁₀O₁₇:Eu²⁺ (BAM). Ca₂B₅O₉Cl:Eu²⁺ is a good blue component phosphor for n-UV excited solid-state lighting.     

Melilite Formation in a Samarium-Stabilized α-Sialon Ceramic during Postsintering Heat Treatments

The formation of the melilite solid solution phase (M'), Sm₂Si_3−xAl_xO_3+xN_4−x, in an α-sialon sample of overall composition Sm_0.6Si_9.28Al_2.69O_1.36N_14.76, was studied as a function of time in the temperature interval 1375–1525°C. The alpha-sialon ceramic contained only minor amounts of the 21R sialon polytype and some residual grain-boundary glass before heat treatment. In situ studies by high-temperature X-ray diffraction were combined with postsintering heat treatment followed by quenching. The M'-phase was found to be formed by two different mechanisms: either crystallization of the residual grain-boundary liquid or a direct decomposition of the α-sialon phase. The liquid crystallized during the first 10–15 min of heat treatment, yielding a rapid M'-phase formation, and further formation of M'-phase continued at a much slower rate, related to the decomposition of α-sialon.     

Subsolidus Phase Relationships in the Ga2O3–Al2O3–TiO2 System

Subsolidus phase relationships in the Ga₂O₃–Al₂O₃–TiO₂ system at 1400°C were studied using X-ray diffraction. Phases present in the pseudoternary system include TiO₂ (rutile), Ga_{2−2 x} Al_{2 x} O₃ ( x ≤0.78 β-gallia structure), Al_{2−2 y} Ga_{2 y} O₃ ( y ≤0.12 corundum structure), Ga_{2−2 x} Al_{2 x} TiO₅ (0≤ x ≤1 pseudobrookite structure), and several β-gallia rutile intergrowths that can be expressed as Ga_{4−4 x} Al_{4 x} Ti _{n −4}O_{2 n −2} ( x ≤0.3, 15≤ n ≤33). This study showed no evidence to confirm that aluminum substitution of gallium stabilizes the n =7 β-gallia–rutile intergrowth as has been mentioned in previous work.     

Synthesis and Luminescence Properties of Orange–Red-Emitting M2Si5N8:Eu2+ (M=Ca, Sr, Ba) Light-Emitting Diode Conversion Phosphors by a Simple Nitridation of MSi2

Eu²⁺-doped M₂Si₅N₈ (M=Ca, Sr, Ba) orange–red phosphors were successfully prepared by a simple, direct, and efficient solid-state reaction using air-stable MSi₂, Eu₂O₃, and α-Si₃N₄ as the starting materials under N₂–H₂ (5%) atmosphere. The influence of the type of the alkaline-earth ion on the phase structure and luminescence properties has been investigated. The results show that the synthesized powders have a single-phase crystal structure of M₂Si₅N₈ for M=Ca, Sr, and a little amount of BaSi₇N₁₀ impurity phase for M=Ba. Under the blue light excitation, M₂Si₅N₈:Eu²⁺ shows a typical broad band emission of Eu²⁺ ranging from orange to red (585–620 nm) depending on the type of M ion. The emission intensity, conversion efficiency, and thermal stability increase with the sequence of Ca2Si₅N₈:Eu²⁺ has the highest application potential as a red conversion phosphor for white light-emitting diodes.     

Polymorphism of BaTiO3 Acceptor Doped with Mn3+, Fe3+, and Ti3+

The effect of Mn doping on the cubic to hexagonal phase transition temperature in BaTiO₃ has been determined by quenching samples with different Mn contents from a range of temperatures. Under conditions of equilibrating samples in air over the range 1000°–1400°C, cubic solid solutions BaTi_{1− x} Mn _x O_3−δ form over the range 0≤ x ≤0.015(5), whereas hexagonal solid solutions form for x ≥0.02, depending on the temperature. The results are compared with those on doping BaTiO₃ with Fe³⁺ and observations made concerning acceptor doping with Ti³⁺.     

Synthesis and Consolidation of BaAl2Si2O8:Eu: Development of an Integrated Process for Luminescent Smart Ceramic Materials

A novel, integrated, fast, and inexpensive process for the preparation of dense Ba_{(1− x )}Eu _x Al₂Si₂O₈ thin ceramic specimens for damage sensor applications is reported. The processing approach involves a combination of combustion synthesis for the preparation of the powders and spark plasma sintering (SPS) for the consolidation of the specimens to densities close to 100% of relative density. The synthesis of the porous powders by combustion resulted in particle (agglomerate) sizes that were on average 421 nm, as determined from dynamic light scattering, and in the almost complete reduction of the initial Eu³⁺ activators to Eu²⁺. The powders densified to grain sizes of around 250 nm due to a collapse of the porous powder structure and minimal grain growth during SPS. Thermal treatment of the powders and sintered specimens improved the intensity of the emissions at 373 and 745 nm and diminished the emission at 485 nm. The luminescence phenomena from the specimens were a result of two mechanisms: (1) the removal of strain in the lattice due to thermal treatment, and (2) a charge transfer mechanism between Eu²⁺ and Eu³⁺.     

Comparison of the Luminescence Properties of Dy3+ in α-Sialon and Oxynitride Glass

Dy-α-sialon and β-Si₃N₄ materials containing Dy-oxynitride glass were hot pressed at 1800°C for 1 h. The luminescence spectra of Dy³⁺ in these samples were compared when excited at 350 nm. The results showed that two strong emission bands in the region 470–500 nm and 570-600 nm, associated with the ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺ ions, were observed in Dy-α-sialon. However, no emission peak was detected from the β-Si₃N₄ sample, despite it containing the same amount of Dy³⁺ cations. This proved that only the Dy³⁺ cations in the α-sialon structure, not those in the oxynitride glass, produce the luminescence spectrum.     

New Red- and Green-Emitting Phosphors, AYP2O7.5:RE3+ (A=Ca and Sr; RE=Eu and Tb) under Near-UV Irradiation

New red- and green-emitting phosphors, AY_{1− x} P₂O_7.5: x RE³⁺ (A=Ca and Sr; x =0.01, 0.03, 0.05, 0.10; RE=Eu and Tb) were synthesized by the conventional ceramic route and their photoluminescence properties under near-ultraviolet (UV) irradiation were investigated. It was found that CaYP₂O_7.5: Eu³⁺ phosphor emits strong red light when excited by a radiation of 394-nm wavelength and SrYP₂O_7.5:Eu³⁺ gives intense orange light when excited by a radiation of 396-nm wavelength. Strong green emission for AY_{1− x} P₂O_7.5:Tb³⁺ is also observed under near-UV irradiation (378 nm). When compared with emission intensity from a standard YPO₄:0.05Tb³⁺, the emission from SrYP₂O_7.5:0.05Tb³⁺ showed greater intensity values under the same excitation wavelength (378 nm). X-ray powder diffraction analysis showed that AYP₂O_7.5 has xenotime-type structure.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

A Potential Red-Emitting Phosphor BaGd2(MoO4)4:Eu3+ for Near-UV White LED

Red-emitting phosphor BaGd_{2− x} Eu _x (MoO₄)₄ has been successfully synthesized by a simple sol–gel method. The process of phosphor formation is characterized by thermogravimetric-differential thermal analysis and X-ray diffraction. Field-emission scanning electronic microscopy is used to characterize the size and the shape of the phosphor particles. Photo-luminescent property of the phosphor is also performed at the room temperature. The effects of firing temperature and Eu³⁺ activator concentration on the photoluminescence (PL) properties are elaborated in detail. PL characterization reveals that the sample with the firing temperature at 800°C and the concentration of Eu³⁺ at 0.7 shows the most intense emission, and its intensity is about three times stronger than that of phosphor prepared by solid-state method with the same composition and firing temperature. The new red-emitting phosphor shows an intense absorption at 396 nm, which matches well with commercial near-UV light-emitting diode (LED) chips, therefore, it is a good candidate of red phosphor used for near-UV white LEDs.     

Enhanced Phase Stability and Photoluminescence of Eu3+ Modified t-ZrO2 Nanoparticles

Tetragonal ( t ) ZrO₂ nanoparticles have been obtained by a partial Eu³⁺→Zr⁴⁺ substitution, synthesized using a simple oxalate method at a moderate temperature of 650°C in air. The Eu³⁺ additive, 2 mol% used according to the optimal photoluminescence (PL), gives small crystallites of the sample. On raising the temperature further, the average crystallite size D grows slowly from 16 nm to a value as big as 49 nm at 1200°C. The Eu³⁺: t -ZrO₂ nanoparticles have a wide PL spectrum at room temperature in the visible to near-IR regions (550–730 nm) in the ⁵D₀→⁷F_J (Eu³⁺), J =1–4, electronic transitions. The intensity of the ⁵D₀→⁷F₄ group is as large as that of the characteristic ⁵D₀→⁷F₂ group of the spectrum in the forced electric-dipole allowed transitions. The enhanced t -ZrO₂ phase stability and wide PL can be attributed to the combined effects of an amorphous Eu³⁺-rich surface and part of the Eu³⁺ doping of ZrO₂ of small crystallites.     

Effect of V2O5 Doping on the Sintering and Dielectric Properties of M-Phase Li1+x−yNb1−x−3yTix+4yO3 Ceramics

The effect of the addition of V₂O₅ on the structure, sintering and dielectric properties of M -phase (Li_{1+ x − y} Nb_{1− x −3 y} Ti _x +4 _y )O₃ ceramics has been investigated. Homogeneous substitution of V⁵⁺ for Nb⁵⁺ was obtained in LiNb_{0.6(1− x )}V_{0.6 x} Ti_0.5O₃ for x ≤ 0.02. The addition of V₂O₅ led to a large reduction in the sintering temperature and samples with x = 0.02 could be fully densified at 900°C. The substitution of vanadia had a relatively minor adverse effect on the microwave dielectric properties of the M -phase system and the x = 0.02 ceramics had [alt epsilon]_r= 66, Q × f = 3800 at 5.6 GHz, and τ_f= 11 ppm/°C. Preliminary investigations suggest that silver metallization does not diffuse into the V₂O₅-doped M -phase ceramics at 900°C, making these materials potential candidates for low-temperature cofired ceramic (LTCC) applications.     

Microwave Dielectric Properties and Far-Infrared Reflectivity Characteristics of the CaTiO3–Li(1/2)−3xSm(1/2)+xTiO3Ceramics

Microwave dielectric properties and far-infrared reflectivity spectra of the 0.3CaTiO₃–0.7Li_{(1/2)−3 x} Sm_{(1/2)+ x} TiO₃ ceramics were investigated as a function of Sm³⁺ substitution (0.0 ≤ x ≤ 0.12). The dielectric constant decreased as the Sm³⁺ substitution increased. The Q × f value increased, up to a solid-solution limit at x = 0.11, because of the change of vibration modes between the A-site cation and the TiO₆ octahedron, and then decreased because of the formation of a secondary phase (Sm₂Ti₂O₇). On the analysis of the far-infrared reflectivity spectra, in the 50–4000 cm⁻¹ range, the change of the dielectric loss and dielectric constant could be explained by the intrinsic factor.     

Improved Fluorescence from Tm-Ho- and Tm-Ho-Eu-Codoped Transparent PbF2 Glass-Ceramics for S+-Band Amplifiers

Tm³⁺-Ho³⁺- and Tm³⁺-Ho³⁺-Eu³⁺-ion-codoped oxyfluoride transparent glass-ceramics containing PbF₂ nanocrystals were prepared, and the near-infrared fluorescence properties of the Tm³⁺ ions were investigated for their potential use as a 1.4 μm amplifier. For all samples, the lifetime of the Tm³⁺:³ H ₄ level increased with heat treatment because of the decrease of the phonon energy as PbF₂ crystals were formed. Moreover, it was revealed that codoping with Ho³⁺ or Eu³⁺ was effective in suppressing the lifetime of the Tm³⁺:³ F ₄ level by energy transfer to the Ho³⁺:⁵ I ₇ or Eu³⁺:⁷ F ₆ level. For the codoped samples, the heat treatments decreased the Tm³⁺:³ F ₄ lifetime and increased the Tm³⁺:³ H ₄ lifetime. This was attributed to the concentration of rare-earth ions in the fluoride crystallites. These properties improved the population inversion of the 1.4 μm transition.