Solvent and surfactant effect on the self-assembly and luminescence properties of ZrO2:Eu3+ nanoparticles

ZrO₂:Eu³⁺ nanocrystals ranging from 17 to 43 nm were prepared by the facile precipitation method with a hydrothermal process. The crystallite size was strongly influenced by the solvent composition and enhanced with the presence of surfactant. The use of ethanol combined with surfactant stabilizes 50 wt% of the monoclinic phase, while the use of water only results in 100 wt% tetragonal phase. 80% of nanobelts were obtained preparing the sample with ethanol and surfactant as a results of the self-assembly of nanoparticles. The photoluminescence emission peak centered at 606 nm dominates the emission band for nanobelts, while for nanoparticles it is dominated by a peak centered at 612 nm. Such differences were explained in terms of the site symmetry occupying Eu³⁺ in the host that in turn depends on the crystalline phase. Changes in the intensity ratio I(612 nm)/I(606 nm) is proposed as a tool to analyzing changes in the monoclinic/tetragonal phase composition. The calculated asymmetry ratio R=⁷F₂/⁷F₁～1.2 suggest a high degree of crystallinity of the prepared samples.     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

Band gap control and photoluminescence properties of Ba(Co2x Ti1−x )O3 thin films prepared by Sol–gel method

This paper reports on the preparation, characterization and optical properties of transparent Ba(Co_2x Ti_1?x )O₃ (0 ≤ x ≤ 0.06) thin films prepared by sol–gel method and deposited on fused quartz substrate by spin-coating technique. Their formation is confirmed by X-ray diffraction patterns, energy dispersive X-ray spectrometry and Fourier transformed infrared measurements. Hitherto unreported near-band-gap photoluminescence in ultraviolet, at 378 nm (3.28 eV), of exciton origin is observed which remains unaffected with change in excitation wavelength from 320 to 350 nm. A weak defect emission appears in green region. For larger excitation wavelength, i.e., 488 nm, emission arising from localized states again occurs in green region but with lower energy. The occurrence of efficient violet–blue PL emission is related to ‘direct’ band gap and shallow levels with high optical band gap values. Analysis of band gap variation with dopant concentration, determined using Tauc’s plot assuming them both of ‘direct’ and ‘indirect’ nature, also indicates the ‘direct’ nature. Co⁺² ions as dopants promote a decrease of band gap of films linearly. Scanning electron micrographs show the granular and flakes-like surface growth. Atomic force microscopy images show the presence of ribbon-like nanostructured grains throughout the surface of the films which is smooth with small values of surface roughness.     

Highly Luminescent Material Based on Alq3:Ag Nanoparticles

Tris (8-hydroxyquinoline) aluminum (Alq₃) is an organic semiconductor molecule, widely used as an electron transport layer, light emitting layer in organic light-emitting diodes and a host for fluorescent and phosphorescent dyes. In this work thin films of pure and silver (Ag), cupper (Cu), terbium (Tb) doped Alq₃ nanoparticles were synthesized using the physical vapor condensation method. They were fabricated on glass substrates and characterized by X-ray diffraction, scanning electron microscope (SEM), energy dispersive spectroscopy, atomic force microscope (AFM), UV-visible absorption spectra and studied for their photoluminescence (PL) properties. SEM and AFM results show spherical nanoparticles with size around 70–80 nm. These nanoparticles have almost equal sizes and a homogeneous size distribution. The maximum absorption of Alq₃ nanoparticles is observed at 300 nm, while the surface plasmon resonant band of Ag doped sample appears at 450 nm. The PL emission spectra of Tb, Cu and Ag doped Alq₃ nanoparticles show a single broad band at around 515 nm, which is similar to that of the pure one, but with enhanced PL intensity. The sample doped with Ag at a concentration ratio of Alq₃:Ag?=?1:0.8 is found to have the highest PL intensity, which is around 2 times stronger than that of the pure one. This enhancement could be attributed to the surface plasmon resonance of Ag ions that might have increased the absorption and then the quantum yield. These remarkable result suggest that Alq₃ nanoparticles incorporated with Ag ions might be quite useful for future nano-optoelectronic devices.     

Spectroscopy of Nickel-Doped Zinc Sulfide Nanoparticles

ABSTRACT

In the present study, Zn_1?xNi_xS (x = 0.0–0.8 mol%) nanoparticles were prepared through the chemical route and the synthesis involved the mixing and drying of zinc acetate and sodium sulphide in an appropriate ratio with the addition of Ni²⁺ at a proper concentration. The structural and spectroscopic studies are investigated by X-ray diffraction (XRD), absorption spectra, emission and excitation spectra, and Raman spectra. Compared with that of the pristine materials, the absorption band-edge demonstrates an apparently blue shift, which is attributed to the quantum size effect. The average particle size of ZnS nanoparticles is in the range of 2–4 nm deduced from the XRD line broadening. Excited at about 330 nm, a blue emission band at 425 nm can be observed, which corresponds to Ni²⁺ luminescent center; this result is consistent with the postulation that Ni²⁺ replaced the Zn²⁺ ions in the lattice of ZnS nanocrystals. Excitation spectra also confirm the above postulation. The effect of different concentrations of nickel is also studied by Raman spectra.     

Metal Quinolates as Phosphors for PC-LED Applications

Metal quinolates, Liq Alq₃ Znq₂ Mgq₂ exhibit efficient luminescence in blue green region and find applications as emission layer in OLEDs. In most of these quinolates the excitation spectra are broad in the range 350 to 410 nm, just short of emission spectra of efficient GaN based blue LEDs. In this paper we report metal quinolates synthesized by slightly modified method in which the excitation gets extended beyond 450 nm so that there is better overlap between emission spectra of blue LED and the excitation spectra. Therefore these phosphors may be used for PC-LED applications.     

Effect of ZnO sacrificial layer thickness on the structure and optical properties of GaN nanoparticles prepared by RF magnetron sputtering

GaN nanoparticles were prepared on sapphire (0001) substrates with ZnO sacrificial layers by self assembly of Ga₂O₃ films in their reaction with NH₃. ZnO sacrificial layers with different thicknesses and Ga₂O₃ films were deposited on sapphire substrates in turn by a radio frequency (RF) magnetron sputtering system. Nitridation of the Ga₂O₃ films was then carried out in a quartz tube furnace. The effect of ZnO sacrificial layer thickness on the structure and optical properties of nanoparticles prepared by RF magnetron sputtering were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and photoluminescence (PL). GaN nanoparticles with ZnO sacrificial layers of different thicknesses possess hexagonal wurtzite crystal structure and have a preferred orientation with c axis perpendicular to the sapphire substrates. XRD, SEM, and AFM results reveal that the better-crystallinity, uniform, and well-dispersed GaN nanoparticles (～30 nm) without agglomeration were obtained with a ZnO sacrificial layer 300-nm thick. The PL result reveals that the optical properties of the GaN nanoparticles are improved with a ZnO sacrificial layer 300-nm thick. Therefore, we suggest that a ZnO sacrificial layer 300-nm thick is the most suitable condition for obtaining better-quality GaN nanoparticles with good luminescence performance. Moreover, the mechanism of the formation of GaN nanoparticles with ZnO sacrificial layers is also discussed.     

Gallium nitride nanoparticle synthesis using nonthermal plasma with gallium vapor

Gallium nitride (GaN) nanoparticles are synthesized by the gallium particle trapping effect in a N₂ nonthermal plasma with metallic Ga vapor. A proposed method has an advantage of synthesized GaN nanoparticle purity because the gallium vapor from the inductively heated tungsten boat does not contain any impurity source. The synthesized particle size can be controlled by the amount of Ga vapor, which is adjusted using the plasma emission ratio of nitrogen to gallium, owing to the particle trapping effect. The synthesized nanoparticles are investigated by electron microscopy studies. High-resolution transmission electron microscopy (HRTEM) studies confirm that the synthesized GaN nanoparticles (10–40 nm) crystallize in a single-phase wurtzite structure. Room-temperature photoluminescence (PL) measurements indicate the band-edge emission of GaN at around 378 nm without yellow emission, which implies that the synthesized GaN nanoparticles have high crystallinity.     

Hydrothermal synthesis of MnO2 nanowires: structural characterizations,optical and magnetic properties

In this paper, 1D single-crystalline MnO₂ nanowires have been successfully synthesized by hydrothermal method using KMnO₄ and (NH₄)₂S₂O₈ as raw materials. X-ray diffraction patterns and high-resolution TEM images reveal pure tetragonal MnO₂ phase with diameters of 15–20 nm. Photoluminescence studies exhibited a strong ultraviolet (UV) emission band at 380 nm, blue emission at 452 nm and an extra weak defect-related green emission at 542 nm. UV–visible spectrophotometery was used to determine the absorption behavior of nanostructured MnO₂ and a direct optical band gap of 2.5 eV was acquired by Davis–Mott model. The magnetic properties of the products have been evaluated using vibrating sample magnetometer, which showed that MnO₂ nanowires exhibited a superparamagnetic behavior at room temperature. The magnetization versus temperature curve of the as-obtained MnO₂ nanowires shows that antiferromagnetic transition temperature is 99 K.     

A novel method to synthesize ordered porous SnO2 nanostructures and their optical properties

Three-dimensional porous ordered SnO₂ nanostructures have been fabricated by templating a sol–gel precursor solution against the polystyrene nanospheres for the first time. Field emission scanning electron micrography (FESEM) indicates that the surface of the nanostructures is highly regular and the porous structures are perfectly ordered. Besides a broad emission band at 600 nm, the porous SnO₂ nanostructures show an additional emission band at 430 nm, which is seldom seen in the bulk SnO₂ materials. Spectral examinations and analyses reveal that the 430 nm band is induced by the interfacial effects between the porous frameworks.     

Quantum Effect on the Energy Levels of Eu2+ Doped K2Ca2(SO4)3 Nanoparticles

Quantum confinement effect on the energy levels of Eu²⁺ doped K₂Ca₂(SO₄)₃ nanoparticles has been observed. The broad photoluminescence (PL) emission band of Eu²⁺ doped K₂Ca₂(SO₄)₃ microcrystalline sample observed at ～436 nm is found to split into two narrow well resolved bands, located at 422 and 445 nm in the nanostructure form of this material. This has been attributed to the reduction in the crystal field strength of the nanomaterials, which results in widening the energy band gap and splitting the broad 4f⁶5d energy level of Eu²⁺. Energy band gap values of the micro and nanocrystalline K₂Ca₂(SO₄)₃ samples were also determined by measuring the UV–visible absorption spectra. These values are 3.34 and 3.44 eV for the micro and nanocrystalline samples, respectively. These remarkable results suggest that activators having wide emission bands might be subjected to weak crystal strength via nanostructure materials to modify their electronic transitions. This might prove a powerful technique for producing new-advanced materials for use in the fields of solid state lasers and optoelectronic devises.     

Luminescence spectroscopy of Ce3+-doped ABaPO4 (A=Li, Na, K) phosphors

Ce³⁺ doped ABaPO₄ (A=Li, Na, K) phosphors were prepared by conventional high temperature solid-state reaction. The phosphors were investigated by XRD, photoluminescence excitation and emission spectra, and luminescence decay curves. The five 5d levels corresponding to the 4f¹→4f⁰5d¹ transition of Ce³⁺ ions were identified. The spectroscopic parameters, e.g., the 5d barycenter, the crystal-field splitting, and the Stokes shift, were discussed. LiBaPO₄:Ce³⁺ phosphor could be efficiently excited by the near-UV lights (330–420 nm) and showed a broad emission band in the range of 430–620 nm with the maximum wavelength at 468 nm. In contrast, Ce³⁺-doped NaBaPO₄ and KBaPO₄ showed only excitation bands in a limited UV region (230–370 nm) and have blue emission at 385 nm and 416 nm, respectively. The temperature quenching of luminescence and the chromaticity coordinates were reported. The luminescence properties were discussed by analyzing the crystal structure and the local surroundings of Ce³⁺ ions on the Ba²⁺ sites.     

Multilayer based interferential-plasmonic structure: metal cluster 3D grating combined with dielectric mirror

This paper reports strong deep-ultraviolet and visible photoluminescence (PL) of the GaN nanoparticles depending on the conversion time from Ga₂O₃ to GaN. Monoclinic β-Ga₂O₃ nanoparticles with a diameter of approximately 2.5–5.0 nm were fabricated prior to conversion to GaN. The Ga₂O₃ nanoparticles were converted to GaN in the tube furnace with NH₃ flow at 900°C for 10, 30, 60, and 120 min. Depending on the conversion time, the converted GaN nanoparticle size became bigger with the increase of the conversion time. The characteristic GaN x-ray diffraction (XRD) peaks became bigger when the conversion time increased. The PL intensity drastically increased with the increase of the conversion time. The spectra profile completely overlapped for GaN samples converted for 10, 30, and 60 min, with the maximum peak at 390 nm. However, the PL spectrum slightly narrowed and red-shifted with the maximum peak at 400 nm for the GaN nanoparticles converted for 120 min.     

Hydrothermal preparation of CuGaS2 crystallites with different morphologies

The CuGaS₂ crystallites with different morphologies were prepared at 160 °C through hydrothermal process by using CuCl, GaCl₃ solution, and thiourea as source materials. The samples were characterized by means of X-ray powder diffraction, element analysis, transmission electron microscopy, and photoluminescence (PL). In present route, as-prepared CuGaS₂ crystallites displayed spherical and whisker-like nanoparticles and snowflake-like micrometer particles. Room temperature PL spectrum of the snowflake-like crystallites exhibits a weak emission band at 540 nm and a broad strong emission band at 735 nm. The role that the reaction media played in the morphologies of the CuGaS₂ crystallites was investigated, and a possible reaction mechanism was proposed.     

Influence of Surface Coating on Structural and Photoluminescent Properties of CaMoO4:Pr Nanoparticles

CaMoO₄:Pr(core), CaMoO₄:Pr@CaMoO₄ (core/shell) and CaMoO₄:Pr@CaMoO₄@SiO₂ (core/shell/shell) nanoparticles were synthesized using polyol method. X-ray diffraction (XRD), thermogravimatric analysis (TGA), UV–vis absorption, optical band gap energy analysis, Fourier transform infrared (FTIR), FT-Raman and photoluminescence (PL) spectroscopy were employed to investigate the structural and optical properties of the synthesized core and core/shell nanoparticles. The results of the XRD indicate that the obtained core, core/shell and core/shell/shell nanoparticles crystallized well at ~150 °C in ethylene glycol (EG) under urea hydrolysis. The growth of the CaMoO₄ and SiO₂ shell (~12 nm) around the CaMoO₄:Pr core nanoparticles resulted in an increase of the average size of the nanopaticles as well as in a broadening of their size distribution. These nanoparticles can be well-dispersed in distilled water to form clear colloidal solutions. The photoluminescence spectra of core, core/shell and core/shell/shell nanoparticles show the characteristic charge transfer emission band of MoO₄ ^2? (533 nm) and Pr³⁺ 4f²?→?4f², with multiple strong ³H₄?→?³P₂, ¹D₂?→?³H₄ and ³P₀?→?³?F₂ transitions located at ~490, 605 and 652 nm, respectively. The emission intensity of the CaMoO₄:Pr@CaMoO₄ core/shell and CaMoO₄:Pr@CaMoO₄@SiO₂ core/shell/shell nanoparticles increased ~4.5 and 1.7 times,respectively, with respect to those of CaMoO₄:Pr core nanoparticles. This indicates that a significant amount of nonradiative centers existing on the surface of CaMoO₄:Pr@CaMoO₄ core/shell nanoparticles can be eliminated by the shielding effect of CaMoO₄ shells.     

Optical and EPR Properties of Mn- and Eu-Activated LaMgAl11O19 Phosphor

LaMgAl₁₁O₁₉ phosphor doped with Eu and Mn ions has been prepared by the urea combustion route. The as-prepared phosphor was studied using X-ray diffraction, electron paramagnetic resonance (EPR), diffuse reflectance and photoluminescence studies. The EPR spectra of LaMgAl₁₁O₁₉:Eu, Mn phosphor exhibit signals with the effective g values at g = 1.98, 4.29 and 7.23. The resonance signals at g = 1.98 and 4.29 were attributed to Mn²⁺ ions in tetrahedral and rhombic environment, respectively. The resonance signal at g = 7.23 was attributed to Eu²⁺ ions. The optical spectrum of this phosphor exhibits an intense band in the visible region and this band has been attributed to spin-allowed ⁵E_g → ⁵T_2g transition of Mn³⁺ ions. Upon excitation at 324 nm, the material displays emission in the blue, green and red spectral region.     

Luminescent Fluorene-Based Bis-Pyrazolyl Aniline Ligand for Aluminum Detection

The design, synthesis, and photophysical properties of a new fluorene-based fluorescent chemosensor, 4-((E)-2-(2-(benzo[d]thiazol-2-yl)-9,9-diethyl-9H-fluoren-7-yl)vinyl)-N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzenamine (AXF-Al), is described for the detection of Al³⁺. AXF-Al exhibited absorption at 382 nm and strong fluorescence emission at 542 nm (fluorescence quantum yield, Φ _F, of 0.80). The capture of Al³⁺ by the pyrazolyl aniline receptor resulted in nominal change in the linear absorption (372 nm) but a large hypsochromic shift of 161 nm in the fluorescence spectrum (542 to 433 nm, Φ _F?=?0.88), from which Al³⁺ was detected both ratiometrically and colorimetrically. The addition of other metal ions, namely Mg²⁺, Ca²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg ²⁺ and Pb²⁺, produced only minimal changes in the optical properties of this probe. The emission band of this probe was also accessed by two-photon excitation in the near-IR, as two-photon absorption (2PA) is important for potential applications in two-photon fluorescence microscopy (2PFM) imaging. The 2PA cross section of the free fluorenyl ligand AXF-Al was 220 GM at 810 nm and 235 GM at 810 nm for the Al-ligand complex, practically useful properties for 2PFM.     

MOVPE 生长GaN薄膜的 光致黄带发光与激发光源的相关性

用四种不同光源作为激发光源,研究了蓝宝石衬底金属有机物汽相外延方法生长的氮化镓薄膜的光致发光特性。结果发现用连续光作为激发光源时,光致发光谱中除出现365 nm的带边发射峰外,同时观察到中心波长位于约550 nm 的较宽黄带发光;而用脉冲光作为激发光源时其发光光谱主要是365 nm附近的带边发光峰,未观察到黄带发光。氮化镓薄膜的光致发光特性依赖于所用的激发光源性质。     

Synthesis and microstructure of Co/Ni: MgGa<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

This report discusses the preparation and microstructure of Co/Ni co-doped MgGa₂O₄ nanoparticles. The nanoparticles with the size of 20–55 nm were synthesized by sol-gel method. The phase and crystallinity were confirmed by X-ray powder diffraction (XRD) pattern. The particle size was estimated according to XRD data and transmission electron microscopy. The electronic structure was studied using X-ray photoelectron spectroscopy (XPS). The XPS studies showed that Ga³⁺ ions possess tetrahedral and octahedral sites of spinel structure and the inverse degree (two times of the fraction of tetrahedral Ga³⁺ ions) has increased with the increase of the doping concentration of Co²⁺ and Ni²⁺ ions. For Co/Ni co-doped MgGa₂O₄, two broad absorption bands of 350~500 and 550~700 nm were observed in the absorption spectra. The broad band at 350~500 nm was assigned to the combination of the absorption of octahedral Co²⁺ and Ni²⁺ ions, whereas the absorption band at 550~700 nm is mainly due to tetrahedrally coordinated Co²⁺ ions and octahedrally coordinated Ni²⁺ ions.     

Concentration quenching of Eu<Superscript>2+</Superscript> in a novel blue–green emitting phosphor: Ba<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript>

A novel blue–green emitting phosphor Ba₂ZnSi₂O₇: Eu²⁺ was prepared by a combustion synthesis (CS) method. An efficient green emission under conditions ranging from ultraviolet to visible light was observed. The emission spectrum shows a single intensive band centered at 503 nm, which corresponds to the 4f ⁶5d ¹→4f ⁷ transition of Eu²⁺. The excitation spectrum is a broad band extending from 260 to 465 nm, which matches the emission of ultraviolet light-emitting diodes (UV-LEDs). The critical quenching concentration of Eu²⁺ in Ba₂ZnSi₂O₇:Eu²⁺ phosphor is about 0.05 mol. The corresponding concentration quenching mechanism is verified to be a dipole–dipole interaction. The value of the critical transfer distance is calculated as 19 Å, which is in good agreement with the value (20 Å) derived from the experimental data.