Synthesis of monodisperse spherical core-shell SiO2-SrAl2Si2O8: Eu2+ phosphors by hydrothermal homogeneous precipitation method

Abstract

Nanocrystalline SrAl₂Si₂O₈ :Eu²⁺ phosphor layers were coated on nonaggregated, monodisperse and spherical SiO₂ particles using a hydrothermal homogeneous precipitation. After annealing at 1100 °C, core-shell SiO₂@SrAl₂Si₂O₈ :Eu²⁺ particles were obtained. They were characterized with x-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. XRD analysis confirmed the formation of SiO₂ @SrAl₂Si₂O₈ :Eu²⁺ particles; it indicated that the SrAl₂Si₂O₈ :Eu²⁺ shells on SiO₂ particles consisted of hexagonal crystallites. The core-shell phosphors obtained are well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the coated layer is approximately 20–40 nm. Under ultraviolet excitation (361 nm), the particles emit blue light at about 440 nm due to the Eu²⁺ ions in their shells.     

Self-assembly of monodisperse SiO2-zinc borate core-shell nanospheres for lubrication

Spherical SiO₂ particles have been successfully coated with zinc borate layers through a self-assembly process. The resulted SiO₂-Zn₅B₄O₁₁ core-shell nanospheres were characterized by X-ray diffraction (XRD), infrared spectra (IR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS). The obtained SiO₂-Zn₅B₄O₁₁ core-shell nanospheres have perfect spherical shape with narrow size distribution (average diameters 50 nm), i.e., the cores with mean diameters of 40 nm and the shells with an average thickness of 5 nm, monodisperse and smooth surface. Moreover, the friction coefficient of the base oil was decreased by the addition of SiO₂-Zn₅B₄O₁₁ core-shell nanospheres.     

Synthesis and luminescent properties of SrAl2O4:Eu green-emitting phosphor for white LEDs

SrAl₂O₄:Eu²⁺ phosphor was prepared by a solid-state reaction in CO-reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of SrAl₂O₄:Eu²⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 7–8 μm. Photoluminescence measurements showed that the phosphor can be efficiently excited by UV–visible light from 350 to 430 nm, and exhibited bright green emission peaked at about 516 nm. Bright green LEDs were fabricated by incorporating the phosphor with an InGaN-based UV chip. All the characteristics indicated that SrAl₂O₄:Eu²⁺ is a good candidate phosphor applied in white LEDs.     

Preparation of SrAl2O4: Eu, Dy nanometer phosphors by detonation method

SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer phosphors were synthesized by detonation method. The particle morphology and optical properties of detonation soot that was heated at different temperatures (600–1100 °C) had been studied systematically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results indicated SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer powders in monoclinic system (a = 8.442, b = 8.822, c = 5.160, β = 93.415) can be synthesized by detonation method, when detonation soot was heated at 600–800 °C. The particle size of SrAl₂O₄: Eu²⁺, Dy³⁺ is 35 ± 15 nm. Compared with the solid-state reaction and sol-gel method, synthesis temperature of the detonation method is lower about 500 and 200 °C respectively. After being excited under UN lights, detonation soot and that heated at 600–1100 °C can emit a green light.     

Luminescence enhancement of Y2O3:Eu and Y2SiO5:Ce,Tb core particles with SiO2 shells

This paper reports on the luminescence and microstructural features of oxide nano-crystalline (Y₂O₃:Eu³⁺) and submicron-sized (Y₂SiO₅:Ce³⁺,Tb³⁺) phosphor cores, produced by two different synthesis techniques, and subsequently coated by an inert shell of SiO₂ using a sol-gel process. The shells mitigate the detrimental effect of the phosphor particle surfaces on the photoluminescence emission properties, thereby increasing luminous output by 20-90%, depending on the core composition and shell thickness. For Y₂O₃:Eu³⁺, uniformly shaped, narrow particle size distribution core/shell particles were successfully fabricated. The photoluminescence emission intensity of core nanoparticles increased with increasing Eu³⁺ activator concentration and the luminescence emission intensity of the core/shell particles was 20-50% higher than that of the core particles alone. For Y₂SiO₅:Ce³⁺,Tb³⁺, the core/shell particles showed enhancement of the luminescence emission intensity of 35-90% that of the core particles, depending on the SiO₂ shell thickness.     

Nanorods of white light emitting Sr2SiO4:Eu2+: microemulsion-based synthesis,EPR, photoluminescence,and thermoluminescence studies

White light emitting Sr₂SiO₄:Eu²⁺ nanoparticles were prepared using reverse micellar route using Tergitol as a surfactant. The systems were characterised by X-ray diffraction, scanning electron microscopy (SEM), photoluminescence, thermoluminescence (TL), and electron paramagnetic resonance (EPR) spectroscopy. SEM shows the formation of silicate nanorods. Two emission bands of bluish-green at 490 nm (S(I)) and of orange-red at 605 nm (S(II)) were observed. The two emission bands are assigned to the 4f–5d transition of Eu²⁺ ions in two different cation sites in α′-Sr₂SiO₄ orthorhombic lattices. Gamma-irradiated Sr₂SiO₄:Eu showed the presence of three TL glow peaks at 437, 487 K and weak peak at 540 K; however, no glow was observed in the undoped sample. Reduction of Eu³⁺ to Eu²⁺ is confirmed by EPR spectroscopy.     

Effects of Zn doping on the structural and luminescent properties of Sr4Si3O8Cl4:Eu phosphors

Sr₄Si₃O₈Cl₄: Eu²⁺ phosphors were synthesized by the solid-reaction at high temperature. The emission intensity reaches a maximum at 0.08 mol% of Eu²⁺ concentration. The present paper mainly focused on the effects of Zn²⁺ on the crystallization behavior and photoluminescence (PL) properties of Sr₄Si₃O₈Cl₄:0.08Eu²⁺. Results suggested that no new phase is introduced by co-doping with a small amount of Zn²⁺ ions, but when co-doped with excessive amount of Zn²⁺ ions, Sr₂ZnSi₂O₇ appears. We find that the co-doping of a small amount of Zn²⁺ could remarkably improve the PL intensity of Sr₄Si₃O₈Cl₄:0.08Eu²⁺. When x = 0.05, the intensity of Sr₄Si₃O₈Cl₄:0.08Eu²⁺,xZn²⁺ was increased up to 2.3 times that of pure Sr₄Si₃O₈Cl₄:0.08Eu²⁺, which could be attributed to the flux effect of Zn²⁺ ions, and the Zn²⁺ doping reduces the opportunities of the energy transfer between Eu²⁺.     

Sr3.5Mg0.5Si3O8Cl4: Eu bluish-green-emitting phosphor for NUV-based LED

Sr₄Si₃O₈Cl₄:Eu²⁺ and Sr_3.5Mg_0.5Si₃O₈Cl₄:Eu²⁺ phosphors were prepared by a conventional solid state reaction (SS). Excited by 370 nm near-ultraviolet light, the phosphors show an efficient bluish-green wide-band emission centering at 484 nm, which originates from the 4f5d¹ → 4f⁷ transition of Eu²⁺ ion. The excitation spectra of the phosphors are a broad band extending from 250 nm to 400 nm. Mg²⁺-codoping greatly enhances the bluish-green emission of the phosphors. An LED was fabricated by coating the Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ phosphor onto an ~ 370 nm-emitting InGaN chip. The LED exhibits bright bluish-green emission under a forward bias of 20 mA. The results indicate that Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ is a candidate as a bluish-green component for fabrication of NUV-based white LEDs.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

Near UV-based LED fabricated with Ba5SiO4(F,Cl)6:Eu as blue- and green-emitting phosphor

A series of halosilicate phosphor, Ba₅SiO₄(F,Cl)₆:Eu²⁺, were synthesized by a solid state reaction. Excited by 370-nm light, Ba₅SiO₄Cl₆:Eu²⁺ exhibits a broad emission band peaking at 440 nm. Partial substitution of Cl⁻ with F⁻ in the host lattice leads to red-shift in the emission band with centering wavelength from 440 nm to 503 nm. The possible mechanism for the luminescence change was discussed based on the XRD patterns. Blue and green LEDs were fabricated by combination of a 370 nm-emitting near UV chip and the optimal Ba₅SiO₄Cl₆:Eu²⁺ and Ba₅SiO₄(F₃Cl₃):Eu²⁺, respectively. This series of phosphors is considered as a promising blue and green component used in fabrication of near UV-based white LEDs.     

Synthesis and luminescent characteristic of Eu-doped (Gd,Lu)2O3 nanopowders

Eu³⁺ doped (Gd,Lu)₂O₃ nanopowders with particle sizes ranging from 20 to 70 nm were synthesized by the co-precipitant method using mixed precipitants, namely the mixture of ammonium hydroxide (NH₃⋅H₂O) and ammonium hydrogen carbonate (NH₄HCO₃). The precipitate precursor prepared by this method was believed to possess a basic carbonate composition and its thermal decomposition of the (Gd,Lu)₂O₃:Eu³⁺ powders were investigated by Thermogravimetric analysis and differential thermal analysis (TG-DTA). This preparation was followed by a calcination process at 800-1100 °C and corresponding phosphor structure were examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Photoluminescence measurement of the (Gd,Lu)₂O₃:Eu³⁺ particles show typical red emission at the 612 nm corresponding to the ⁵D₀ → ⁷F₂ transition. We found that the optimal Eu³⁺ molar doping concentration, calcined temperature and reaction time were 7 mol%, 1000 °C, and 2 h, respectively, which is helpful to obtain the final transparent ceramics with excellent properties.     

Luminescence and energy transfer of Mn co-doped SrSi2O2N2:Eu green-emitting phosphors

Eu²⁺ and Mn²⁺ co-doped SrSi₂O₂N₂ green-phosphors, with promising luminescent properties (examined by their powder diffuse reflection, photoluminescence excitation and emission spectra) suitable for UV converted white LEDs, were produced by high temperature solid-state reaction method. The produced materials exhibited intense broad absorption bands at 220–500 nm and a broad emission band centered at ca. 530 nm, attributed to 4f–5d transitions of Eu²⁺. The emission intensity of Eu²⁺ ions was greatly enhanced by introducing Mn²⁺ ions into SrSi₂O₂N₂:Eu²⁺ due to the energy transfer from Mn²⁺ to Eu²⁺. The energy transfer probability from Mn²⁺ to Eu²⁺ depends strongly on the Mn²⁺ concentration, which is maximized at a Mn²⁺ concentration of 3 mol%. It drastically decreases for higher concentrations. The results indicated that SrSi₂O₂N₂:Eu²⁺, Mn²⁺ is a promising green-emitting phosphor for white-light emitting diodes with near-UV LED chips.     

Low-temperature synthesis of Y2SiO5:Eu powders using mesoporous silica and their luminescence properties

This paper reports the synthesis of Eu³⁺ ions-doped Y₂SiO₅ (Y₂SiO₅:Eu³⁺) powders by mesoporous template route. Using mesoporous silica SBA-15 as silica source, Y₂SiO₅:Eu³⁺ powders were prepared by solid-state reaction at a calcination temperature of 1300 °C without fluxes. The prepared Y₂SiO₅:Eu³⁺ powders were characterized by X-ray diffraction, scanning electron microscope, nitrogen adsorption-desorption isotherms, and photoluminescence spectroscopy. The results show that the crystalline Y₂SiO₅:Eu³⁺ particles are dense and have a morphology similar to SBA-15. The low calcination temperature is attributed to the high reactive activity of SBA-15 with large surface area and non-crystalline structure. The Y₂SiO₅:Eu³⁺ powders prepared at a low calcination temperature show luminescence properties similar to the reported results of Eu³⁺ doped-Y₂SiO₅ samples prepared at high temperatures.     

Synthesis and luminescence properties of monodisperse SiO2@SiO2:Eu3+ microspheres

Monodisperse core–shell structured SiO₂@SiO₂:Eu³⁺ microspheres were synthesized in a seeded growth way. In that way, a thin shell of Eu³⁺-doped silica was grown on the prepared monodisperse silica colloids. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR), thermal analysis (TGA-DSC) and photoluminescence (PL) spectroscopy. The results reveal that the SiO₂ spheres have been successfully coated by SiO₂:Eu³⁺ phosphors and the obtained SiO₂@SiO₂:Eu³⁺ particles have perfect spherical shape with narrow size distribution. Additionally, the monodisperse SiO₂@SiO₂:Eu³⁺ microspheres exhibit considerably strong photoluminescence (PL) of Eu³⁺ under the excitation of 393 nm compared with the SiO₂:Eu³⁺ samples with polydispersed or irregular shapes and sizes obtained by base-catalyzed Stöber method. Furthermore, the PL intensity increases with the increasing of Eu³⁺ concentration in SiO₂ microspheres shell, and concentration quenching occurs when Eu³⁺ concentration exceeds 5.0 mol%.     

Self-assembled 3D flower-like NaY(MoO4)2:Eu microarchitectures: Hydrothermal synthesis, formation mechanism and luminescence properties

Self-assembled 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were successfully synthesized by a glycine-assisted hydrothermal method at 180 °C. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were employed to characterize the as-obtained products. It was found that morphology modulation could be easily realized by changing the time of hydrothermal reaction system. 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were formed with 72 h reaction time. The formation mechanism for flower-like architecture was proposed on the basis of a series of time-dependent experiments. The NaY(MoO₄)₂:Eu³⁺ powders obtained can be effectively excited by 396 nm light, and exhibit strong red emission around 615 nm, attributed to the Eu³⁺⁵D₀ → ⁷F₂ transition. An investigation on the photoluminescence (PL) properties of NaY(MoO₄)₂:Eu³⁺ obtained revealed that the luminescence properties were correlated with the morphology and size.     

Influence of calcination temperature on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol–gel-combustion processing

The detailed preparation process of Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ phosphor powders with red long afterglow by sol–gel-combustion method in the reducing atmosphere is reported. X-ray diffraction, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the effects of synthesis temperature on the crystal characteristics, morphology and luminescent properties of the as-synthesized Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors. The results reveal that Sr₃Al₂O₆ crystallizes completely when the combustion ash is sintered at 1200 °C. The excitation and the emission spectra indicate that the excitation broad-band lies chiefly in visible range and the phosphor powders emit strong light at 618 nm under the excitation of 472 nm. The light intensity and the light-lasting time of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors are increased when increasing the calcination temperatures from 1050 to 1200 °C. The afterglow of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors sintered at 1200 °C lasts for over 600 s when the excited source is cut off. The red emission mechanism is discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions.     

Synthesis and optical properties of luminescent core-shell structured silicate and phosphate nanoparticles

Monodisperse, luminescent core-shell structured inorganic nanoparticles were synthesized by sol-gel technology. They exhibit an amorphous SiO₂ core and a crystalline luminescent shell. Zn₂SiO₄:Mn²⁺ and Ca₁₀(PO₄)₆OH:Eu³⁺ shell materials are investigated. The influence of the doping concentration on optical and structural properties was studied. The resulting nanoparticles were characterized by X-ray diffraction analysis, transmission electron microscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy.     

M2Si5N8:Eu-based (M = Ca, Sr) red-emitting phosphors fabricated by nitrate reduction process

M₂Si₅N₈:Eu²⁺-based (M = Ca, Sr) red-emitting phosphors were fabricated at relatively low temperature (1200 °C) and atmospheric pressure using a simple solid-state reaction process. Several processing parameters were systematically investigated to optimize the phosphors structural characterization and photoluminescence performance, including the amount of europium and the properties of the precursor and activated materials. The as-prepared M₂Si₅N₈:Eu²⁺-based (M = Ca, Sr) phosphors were orange in color and emitted intensively in the red region of 580-670 nm under 465 nm excitation. This simple fabrication technique can be readily used for the optimization of phosphor microstructures and high-performance red-emitting phosphors since it eliminates many air-sensitive precursors.     

Influence of excitation wavelengths on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol-gel-combustion processing

Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ red-emitting long afterglow phosphor was synthesized by sol-gel-combustion methods using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, Eu₂O₃, Dy₂O₃, H₃BO₃ and C₆H₈O₇·H₂O as raw materials. The crystalline structure of the phosphors were characterized by X-ray diffraction, luminescent properties of phosphors were analyzed by fluorescence spectrophotometer. The effect of excitation wavelengths on the luminescent properties of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors was discussed. The emission peak of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor lays at 516 nm under the excitation of 360 nm, and at 612 nm under the excitation of 468 nm. The results reveal that the Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor will emit a yellow-green light upon UV illumination, and a bright red light upon visible light illumination. The emission mechanism was discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions in Sr₃Al₂O₆. The afterglow time of (Sr_0.94Eu_0.03Dy_0.03)₃ Al₂O₆ phosphors lasts for over 600s after the excited source was cut off.     

Photocatalytic degradation of formaldehyde by nanostructured TiO2 composite films

Interest in the photocatalytic oxidation of formaldehyde from contaminated wastewater is growing rapidly. The photocatalytic activity of the nanocrystalline Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film for the degradation of formaldehyde solution under visible light was discussed in this study. The films were characterised by field emission scanning electron microscopy (FE-SEM) equipped with energy-dispersive spectroscopy, X-ray diffraction (XRD), BET surface area, UV–Vis absorption spectroscopy, and photoluminescence spectroscopy. The FE-SEM results revealed that the Fe³⁺/F^? co-doped TiO₂–SiO₂ film was composed of uniform round-like nanoparticles or aggregates with the size range of 5–10 nm. The XRD results indicated that only the anatase phase was observed in the film. Compared with a pure TiO₂ film and a singly modified TiO₂ film, the Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film showed the best photocatalytic properties due to its strong visible light adsorption and diminished electrons-holes recombination.