Characterization of ZnGa2O4:Mn nanophosphor synthesized by the solvothermal method in 1,4-butanediol-water system

We characterized ZnGa₂O₄:Mn²⁺ (ZnGa₂O₄—zinc gallate) nanophosphor synthesized by the solvothermal method in 1,4-butanediol-containing water to increase the amount of Mn²⁺ ions incorporated in the ZnGa₂O₄ matrix without post-heat treatment. We investigated the influence of water content in the solvent on the photoluminescence (PL) intensity and the Mn amount, the latter being measured by X-ray fluorescence analysis and electron paramagnetic resonance spectroscopy. The PL intensity per Mn amount reached the maximum at the 50 wt% water content. The addition of water promotes repeated dissolution and precipitation, resulting in homogeneous Mn²⁺ distribution in the ZnGa₂O₄ matrix. This suggests that the solvothermal method in the 1,4-butanediol-water system is useful for increasing the amount of Mn²⁺ ions incorporated in the ZnGa₂O₄ matrix without post-heat treatment. At the water content >50 wt%, the decrease in PL intensity is attributed to the optical absorption of the by-product, MnOOH.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Synthesis, characterization and optical properties of water-soluble ZnS:Mn nanoparticles

ZnS nanoparticles with Mn²⁺ doping (0.5-20%) have been prepared through a simple chemical method, namely the chemical precipitation method. The structure of the nanoparticles has been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV-vis spectrometer. The size of the particles is found to be 3-5 nm range. Photoluminescence spectra were recorded for undoped ZnS nanoparticles using an excitation wavelength of 320 nm, exhibiting an emission peak centered at around 445 nm. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn²⁺⁴T₁-⁶A₁ transition is observed along with the blue emission. The prepared Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission 580 nm with the blue emission suppressed. The maximum PL intensity is observed only at the excitation energy of 3.88 eV (320 nm). Increase in stabilizing time up to 48 h in de-ionized water yields the enhancement of emission intensity of doped (4% Mn²⁺) ZnS. The correlation made through the concentration of Mn²⁺ versus PL intensity resulted in opposite trend (mirror image) of blue and yellow emissions.     

Photoluminescence properties of impurity-doped ZnS nanocrystals fabricated by sequential ion implantation

We have studied photoluminescence (PL) spectrum and dynamics of Cu- and Al-doped ZnS (ZnS:Cu,Al) nanocrystals fabricated by sequential implantation of Zn⁺, S⁺, Cu⁺, and Al⁺ ions into Al₂O₃ matrices. These samples exhibit intense green PL under UV light excitation. The space- and time-resolved PL measurements show that the broad green PL is due to the donor–acceptor (DA) pair luminescence of single ZnS:Cu,Al nanocrystals.     

The impact cross section of Er3+ in ZnS

Four kinds of Er³⁺ centers in ZnS:Er³⁺ thin films have been distinguished by means of laser selective excitation. Their impact cross sections in electroluminescence (EL) and absorption cross sections in photoluminescence (PL) have been compared with each other. The average value of the impact cross section of Er³⁺ obtained by comparing the EL intensity of Er³⁺ with that of Mn²⁺ in ZnS:ErF₃, Mn²⁺ thin films is about 2×10⁻¹⁶ cm².     

Surface modification and fluorescent properties of Mn2+-doped and undoped ZnS nanoparticles

Abstract

ZnS nanoparticles and Mn²⁺-doped ZnS nanoparticles were prepared by a reverse micelle reaction system. In addition, ZnS and Mn²⁺-doped ZnS nanoparticles were modified with poly(vinyl alcohol) (PVA) and 1-dodecanethiol (C₁₂H₂₅SH). The average particle size of the ZnS sample is determined around 2.3 nm by using the well-known Scherrer equation, which is in accordance with the results obtained from UV–vis and TEM analysis. Fluorescence intensity of the Mn²⁺-doped ZnS nanoparticles increases with increasing Mn²⁺ content compared with undoped ZnS nanoparticles, and coating PVA can also make fluorescence intensity increase. Different Zn²⁺/S^2- or C₁₂H₂₅SH/Zn²⁺ can affect intensity of PL emission peak and its position, which is discussed in this paper.     

Yellow-orange light emission from Mn2+-doped ZnS nanoparticles

ZnS nanoparticles with Mn²⁺ doping (1–2.5%) have been prepared through a simple soft chemical route, namely the chemical precipitation method. The nanostructures of the prepared undoped ZnS and Mn²⁺-doped ZnS:Mn nanoparticles have been analyzed using X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–vis spectrophotometer. The size of the particles is found to be in 2–3 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample only exhibits a blue-light emission peaked at ∼365 nm under UV excitation. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn^{2+ 4}T₁–⁶A₁ transition is observed along with the blue emission. The prepared 2.5% Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission at ∼580 nm with the blue emission suppressed.     

Effects of doping on the surface energies of nanocrystals and evidence from studies at high pressure

Zn_1−XMn_XS (X=0.85% and 1.26%) nanoparticles have been synthesized using a specially designed equipment and we have studied the influence of doping Mn²⁺ on the surface energy of ZnS. The high pressure behaviors of ZnS nanocrystals with different dopant contents have been investigated using angle-dispersive synchrotron X-ray powder diffraction up to 45.1 GPa. Theoretical calculations show that doping with Mn²⁺ increases the surface energy of the nanocrystals. The theoretical result has been further corroborated by our experimental observation of an increase in the phase transition pressure of Mn²⁺ doped ZnS nanocrystals in diamond-anvil-cell studies.     

Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.     

Preparation and photoluminescent properties of Ni-doped ZrO2 fibers

Ni²⁺-doped ZrO₂ precursor fibers were prepared via sol-gel technique by dry-spinning method and then heat-treated at different temperatures. The surface of the fibers is smooth with uniform diameter and no cracks have been observed by scanning electron microscopy (SEM). The emission intensity reaches a maximum value at 1 mol% Ni²⁺ because of the concentration quenching. The photoluminescence (PL) relative intensity is apparently intensifying with increasing temperature before 700 °C due to the crystallinity of the ZrO₂ lattice improvement. The PL results show that the typical emission center is at 510 nm excited at 315 nm.     

Hydrothermal-assisted ion exchange synthesis and photoluminescence of Li+ and Eu3+ co-doped NaLa(WO4)2 as near-UV type red phosphors

A series of Li⁺ and Eu³⁺ co-doped double tungstate NaLa(WO₄)₂ (NLW) red phosphors have been successfully synthesized by an ion exchange method under a hydrothermal condition. The effects of Li⁺ doping concentration on the crystal structure, morphology and photoluminescence properties were investigated using the XRD, TEM and photoluminescence (PL) measurements. The results reveal that the samples have phase-pure scheelite structure and adopt spherical particle morphology. Furthermore, room temperature PL spectrum shows that the optical brightness is highly dependent on the concentration of doping Li⁺, which is determined by ion exchange duration and the precursor concentration of LiNO₃. As 5% Li⁺ ions was introduced into the crystal lattice, the emission intensity was enhanced by more than 10-fold as compared with the pristine one. Moreover, the co-doping of Li⁺ can substantially improve the effective excitation of the NaLa(WO₄)₂:Eu³⁺ phosphors under near-UV region.     

PL and EL characterizations of ZnO:Eu, Li films derived by sol-gel process

ZnO:Eu³⁺, Li⁺ films prepared by the dip-coating method were characterized by photoluminescence (PL) and electroluminescence (EL). When the ZnO:Eu³⁺, Li⁺ films were excited using UV light with energy corresponding to the band-to-band excitation of the host matrix, the PL spectra showed emissions from both ZnO and Eu³⁺ ions, while their EL spectra showed emissions only from Eu³⁺ ions, and no emission from ZnO could be detected. It is found that the EL emission intensity B is dependent on the applied voltage, B=B_o exp(−bV^−1/2). With increasing frequency, the EL intensity dramatically increases at lower frequencies (<1000 Hz), and then increases gradually at higher frequencies (>1000 Hz).     

Synthesis and characterization of Cu doped ZnS nanoparticles using TOPO and SHMP as capping agents

Undoped and Cu²⁺ doped (0.2-0.8%) ZnS nanoparticles have been synthesized through chemical precipitation method. Tri-n-octylphosphine oxide (TOPO) and sodium hexametaphosphate (SHMP) were used as capping agents. The synthesized nanoparticles have been analyzed using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrometer (FT-IR), UV-vis spectrometer, photoluminescence (PL) and thermo gravimetric-differential scanning calorimetry (TG-DTA) analysis. The size of the particles is found to be 4-6 nm range. Photoluminescence spectra were recorded for ZnS:Cu²⁺ under the excitation wavelength of 320 nm. The prepared Cu²⁺-doped sample shows efficient PL emission in 470-525 nm region. The capped ZnS:Cu emission intensity is enhanced than the uncapped particles. The doping ions were identified by electron spin resonance (ESR) spectrometer. The phase changes were observed in different temperatures.     

Enhanced luminescence of GdTaO4:Eu thin-film phosphors by K doping

The effect of K⁺ ions on GdTaO₄:Eu³⁺ thin-film phosphors was investigated in order to improve their luminescent properties. The GdTaO₄:Eu_0.1, K_x thin films were synthesized by sol-gel process, and characterized through measuring their microstructure and luminescence. The results indicated that photoluminescence (PL) intensity of GdTaO₄:Eu³⁺ film was improved remarkably by K doping. There were two maxima in the curve of PL intensity against K⁺ dopant concentration, where one was improved up to 2.1 times at x = 0.001 and the other was enhanced up to 2.7 times at x = 0.05. The first maximum was regarded as the alteration of the local environment surrounding the Eu³⁺ activator by incorporation of K⁺ ions, and the second maximum was due to the flux effect. Additionally, the luminescence increased with the increase of firing temperature from 800 °C to 1200 °C.     

Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.     

Improved photoluminescence of BaMgAl10O17 blue phosphor prepared by spray pyrolysis

BaMgAl₁₀O₁₇:Eu²⁺ (BAM) blue phosphor particles with improved photoluminescence (PL) intensity under vacuum ultraviolet (VUV) excitation were prepared by a spray pyrolysis process. In order to improve the PL intensity, Er³⁺ and Nd³⁺ ions were used as co-doping elements. The VUV characteristics of BAM:Eu²⁺, M⁺ (M=Er, Nd) were monitored with varying the Er³⁺ and Nd³⁺ content in order to find the optimal co-doping concentration when they were prepared by spray pyrolysis. It was found that doping Er³⁺ or Nd³⁺ enhances the PL intensity of BAM:Eu²⁺ blue phosphor particles. In particular, the M³⁺ doping effect on the PL intensity was pronounced when the prepared BAM:Eu²⁺, M³⁺ particles were excited by 172 nm VUV. The maximum intensity was obtained when the M³⁺ content was 1.0 at% with respect to Ba element. The PL intensity of BAM:Eu²⁺, M⁺ (M=Er³⁺, Nd³⁺) particles was also further improved by producing them in a spherical shape, which was successfully achieved by controlling the spray solution. The optimized BAM:Eu²⁺, M⁺ particles had about 10% higher PL intensity than that of the commercial particles, which are made by a conventional solid-state reaction.     

Enhanced near-infrared luminescence in Y2O3:Yb nanocrystals by codoping with Li ion

Y₂O₃:Yb³⁺ nanocrystals codoping with Li⁺ ions were synthesized by glycine combustion method. Codoping with Li⁺ ions leads to about 12 times enhancement of the photoluminescence (PL) intensity around 1 μm, in terms of the increased lifetimes at 1026 nm from 0.384 ms to 1.42 ms at room temperature. The enhancement in the PL intensity could be mostly attributed to the modification of the local symmetry around Yb³⁺ ions by codoping with Li⁺ ions.     

Luminescence and radiation-induced color centers in anion-defective alumina crystals after high-dose irradiation

A method of UV spectroscopy was used to measure photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra in anion-defective alumina crystals exposed to high doses of gamma-radiation. An additional emission band in the range of 1.6–2.75 eV appears in the exposed crystals. Aggregate F₂-type centers in different charge states are responsible for this band. It was found that growing intensity of PL aggregate centers occurs at doses corresponding to saturation of dose response and is accompanied by a sharp drop in the intensity of F⁺-band in the PL spectrum resulting from combination of F⁺-centers into aggregates. Uncharged F₂-centers are formed when electrons are trapped by F₂⁺ and F₂²⁺-centers. The main role of F⁺-centers in radiation-induced transformations of color centers under high-dose irradiation of anion-defective alumina crystals was indicated.     

Room temperature photoluminescence from Zr-doped sol-gel silica

Intense room-temperature photoluminescence (PL) from the UV to the green region was observed from Zr⁴⁺-doped silica synthesized by a sol-gel process using tetraethoxysilane as the precursor, followed by thermal treatment at 500 °C in air. The wide PL band can be resolved into three components centered at 3.70, 3.25, and 2.65 eV, respectively. The intensity of the 3.25 and 2.65 eV PL bands was greatly enhanced compared with pure sol-gel silica. The 3.70 eV emission was assigned to non-bridging oxygen hole centers, while the 2.65 eV one originated from neutral oxygen vacancies (V_O). The 3.25 eV PL band was most likely associated with E′ centers, as supported by electron spin resonance measurement. It was proposed that the Zr⁴⁺-doping leads to oxygen deficiency in the silica, thus resulting in enhancement of the density of V_O and E′ center defects.