Influence of thiol capping on the photoluminescence properties of L‐cysteine‐, mercaptoethanol‐ and mercaptopropionic acid‐capped ZnS nanoparticles

Mercaptoethanol (ME), mercaptopropionic acid (MPA) and L‐cysteine (L‐Cys) having ‐SH functional groups were used as surface passivating agents for the wet chemical synthesis of ZnS nanoparticles. The effect of the thiol group on the optical and photoluminescence (PL) properties of ZnS nanoparticles was studied. L‐Cysteine‐capped ZnS nanoparticles showed the highest PL intensity among the studied capping agents, with a PL emission peak at 455 nm. The PL intensity was found to be dependent on the concentration of Zn²⁺ and S^2– precursors. The effect of buffer on the PL intensity of L‐Cys‐capped ZnS nanoparticles was also studied. UV/Vis spectra showed blue shifting of the absorption edge. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of capping agent concentration on thermoluminescence and photoluminescence of copper‐doped zinc sulfide nanoparticles

Copper‐doped zinc sulfide (ZnS:Cu) nanoparticles with varying concentrations of capping agent were prepared using a chemical route technique. These particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy and X‐ray diffraction (XRD). Optical absorption studies showed that the absorption edge shifted towards the blue region as the concentration of the capping agent increased. Using effective mass approximation, calculation of the nanoparticle size indicated that effective band gap energy increases with decreasing particle size. The thermoluminescence (TL) properties of sodium hexameta phosphate (SHMP)‐passivated ZnS:Cu nanoparticles were investigated after UV irradiation at room temperature. The TL glow curve of capped ZnS:Cu showed variations in TL peak position and intensity with the change in capping agent concentration. The photoluminescence (PL) spectra of ZnS:Cu nanoparticles excited at 254 nm exhibited a broad green emission band peaking around 510 nm, which confirmed the characteristic feature of Zn²⁺ as well as Cu²⁺ ions as the luminescent centres in the lattice. The PL spectra of ZnS:Cu nanoparticles with increasing capping agent concentrations revealed that the emission becomes more intense and shifted towards shorter wavelengths as the sizes of the samples were reduced. Copyright © 2014 John Wiley & Sons, Ltd.     

Optical and structural characterization of CdS/ZnS and CdS:Cu2+/ZnS core–shell nanoparticles

Core‐shell CdS/ZnS (Zn 0.025?0.125 M) and CdS:Cu²⁺(1%)/ZnS nanoparticles were successfully synthesized using a chemical method. X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR TEM), photoluminescence (PL) and UV/Visible (UV/Vis) techniques were used to characterize the novel CdS/ZnS and CdS:Cu²⁺/ZnS core–shell nanoparticles. All absorption peaks of the synthesized samples were highly blue‐shifted from the bulk CdS and ZnS. Very narrow and symmetric PL emission was observed in the yellow region for core–shell CdS/ZnS. Furthermore, the PL emission of CdS/ZnS was tuned into orange region by incorporate the Cu ion into the core CdS lattice. Copyright © 2013 John Wiley & Sons, Ltd.     

Tuneable luminescence properties of EDTA‐assisted ZnS:Mn nanocrystals from a yellow‐orange to a red emission band

Luminescence technology has been improved with the help of semiconductor nanoparticles that possess novel optical and electrical properties compared with their bulk counterpart. The aim of this study was to design semiconductor nanocrystals in their pure (ZnS) or doped form (ZnS:Mn) with different concentrations of Mn²⁺ ions by a wet chemical route stabilized by ethylenediamine tetra‐acetic acid (EDTA) and to evaluate their luminescence properties. The nanocrystals were characterized by physicochemical techniques such as X‐ray diffraction (XRD), High‐resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), EDS, and ultraviolet (UV)–visible light and photoluminescence (PL) studies. These results showed the presence of cubic phase and spherically shaped nanocrystals. A blue shift with respect to their bulk counterpart was observed. PL emission spectra were observed with a fixed blue peak and the yellow‐orange bands were red shifted towards the red region under the same excitation wavelength. The orange‐red bands were attributed to the radiation transition of electrons in 3d5 unfilled shells of Mn²⁺ ions [⁴T₁(⁴G)‐⁶A₁(⁶S)]; the ZnS matrix varied with Mn²⁺ concentration. Shift and increase in the intensity of the PL and absorption bands were observed with increase in Mn content. The study showed that Mn²⁺‐doped ZnS nanocrystal emission bands can be tuned from the yellow‐orange to the red regions under a controlled synthesis process and could be used as promising luminescent emitters in the biology field upon functionalization with suitable materials. Further studies on construction with various other materials will be useful for practical applications.     

Structural and photoluminescence study of Mn2+‐activated CaYAl3O7 blue phosphors

The structural and photoluminescence properties of CaYAl₃O₇ phosphor material doped with varying concentration of Mn²⁺ have been studied. The phosphor material was synthesized by the combustion method at 500 °C and was characterized using X‐ray diffraction, Fourier transform infrared spectroscopy and photoluminescence spectroscopy (PL). X‐ray diffraction showed that the crystallites have average sizes in the range of ~58–70 nm. Corresponding Fourier transform infrared spectroscopy investigations confirm the phase formation and the presence of aluminate group (Al‐O bands) in CaYAl₃O₇:Mn²⁺ phosphor. Under the excitation at 356 nm wavelength, the PL spectra show the occurrence of two emission peaks obtained in the blue region at 389 nm and 412 nm, which is attributed to the 4 T1(G) → 6A1 transition of Mn²⁺ ion. Upon increasing Mn²⁺ concentration, the relative PL intensity shows an initial decrement followed by an increase displaying the effect of concentration quenching. Overall the results suggest the possibility of using this material in white lighting devices and plasma display panels. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of cubic ZnS microspheres exhibiting broad visible emission for bioimaging applications

Biocompatible ZnS microspheres with an average diameter of 3.85 µm were grown by solvo‐hydrothermal (S‐H) method using water–acetonitrile–ethylenediamine (EDA) solution combination. ZnS microspheres were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), high‐resolution transmission electron microscopy (HRTEM), Fourier transform (FT)‐Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR) techniques. The broad photoluminescence (PL) emissions from 380–580 nm that were seen from the ZnS microspheres attributed to the increase in carrier concentration, as understood from the observed intense Raman band at 257 cm^–1. Cytotoxicity and haemocompatibility investigations of these ZnS microspheres revealed its biocompatibility. ZnS microspheres, along with biological cell lines, were giving visible light emission and could be used for bioimaging applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of temperature on intense green emitting Na2Ca(PO4)F:Mn2+ phosphor

An intense green luminescent Na₂Ca(PO₄)F:Mn²⁺ phosphor has been prepared at high temperature by reduction treatment in a charcoal environment. The emission band of Mn²⁺ was obtained at around 522 nm (green) under 259 nm excitation. Enhancement in emission intensity arising from the thermal treatment is reported. The intense emission of the spectrum was assigned to electronic transitions ⁴T₁ → ⁶A₁ of Mn²⁺ ions. Intense PL emission suggested that temperature employed plays an important role in the present matrix. X‐ray diffraction pattern, photoluminescence and morphology by SEM of the host lattice of phosphors at different temperatures have been reported in this paper. The results obtained show that the present phosphor has potential for application in green emitting phosphors for the lamp industry. Copyright © 2010 John Wiley & Sons, Ltd.     

Luminescence study of monodispersed ZnS nanoparticles

Monodispersed ZnS nanoparticles have been successfully synthesized by a chemical precipitation method in an air atmosphere using polyvinylpyrrolidone (PVP) and sodium hexametaphosphate (SHMP) as surfactants. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT‐IR), UV–Vis optical absorption and photoluminescence (PL) spectra. Prepared surfactants capped ZnS nanoparticles are highly homogeneous and well dispersed. Optical absorption spectra showed a strong blue shift from the uncapped particles due to the quantum confinement effect. The capped ZnS emission intensity is enhanced than more the uncapped particles. The size of the synthesized particles is around 4–6.5 nm range. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermoluminescence and photoluminescence studies on γ‐ray‐irradiated Ce3+,Tb3+‐doped potassium chloride single crystals

Single crystals of KCl doped with Ce³⁺,Tb³⁺ were grown using the Bridgeman–Stockbarger technique. Thermoluminescence (TL), optical absorption, photoluminescence (PL), photo‐stimulated luminescence (PSL), and thermal‐stimulated luminescence (TSL) properties were studied after γ‐ray irradiation at room temperature. The glow curve of the γ‐ray‐irradiated crystal exhibits three peaks at 420, 470 and 525 K. F‐Light bleaching (560 nm) leads to a drastic change in the TL glow curve. The optical absorption measurements indicate that F‐ and V‐centres are formed in the crystal during γ‐ray irradiation. It was attempted to incorporate a broad band of cerium activator into the narrow band of terbium in the KCl host without a reduction in the emission intensity. Cerium co‐doped KCl:Tb crystals showed broad band emission due to the d–f transition of cerium and a reduction in the intensity of the emission peak due to ⁵D₃–⁷F_j (j = 3, 4) transition of terbium, when excited at 330 nm. These results support that energy transfer occurs from cerium to terbium in the KCl host. Co‐doping Ce³⁺ ions greatly intensified the excitation peak at 339 nm for the emission at 400 nm of Tb³⁺. The emission due to Tb³⁺ ions was confirmed by PSL and TSL spectra. Copyright © 2015 John Wiley & Sons, Ltd.     

Eu2+‐induced enhancement of defect luminescence of ZnS

The Eu²⁺‐induced enhancement of defect luminescence of ZnS was studied in this work. While photoluminescence (PL) spectra exhibited 460 nm and 520 nm emissions in both ZnS and ZnS:Eu nanophosphors, different excitation characteristics were shown in their photoluminescence excitation (PLE) spectra. In ZnS nanophosphors, there was no excitation signal in the PLE spectra at the excitation wavelength λ_ex > 337 nm (the bandgap energy 3.68 eV of ZnS); while in ZnS:Eu nanophosphors, two excitation bands appeared that were centered at 365 nm and 410 nm. Compared with ZnS nanophosphors, the 520 nm emission in the PL spectra was relatively enhanced in ZnS:Eu nanophosphors and, furthermore, in ZnS:Eu nanophosphors the 460 nm and 520 nm emissions increased more than 10 times in intensity. The reasons for these differences were analyzed. It is believed that the absorption of Eu²⁺ intra‐ion transition and subsequent energy transfer to sulfur vacancy, led to the relative enhancement of the 520 nm emission in ZnS:Eu nanophosphors. In addition, more importantly, Eu²⁺ acceptor‐bound excitons are formed in ZnS:Eu nanophosphors and their excited levels serve as the intermediate state of electronic relaxation, which decreases non‐radiative electronic relaxation and thus increases the intensity of the 460 nm and 520 nm emission dramatically. In summary, the results in this work indicate a new mechanism for the enhancement of defect luminescence of ZnS in Eu²⁺‐doped ZnS nanophosphors. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis,characterization and optical properties of polymer‐based ZnS nanocomposites

Nanostructured polymer–semiconductor hybrid materials such as ZnS–poly(vinyl alcohol) (ZnS–PVA), ZnS–starch and ZnS–hydroxypropylmethyl cellulose (Zns–HPMC) are synthesized by a facile aqueous route. The obtained nanocomposites are characterized using various techniques such as X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV/vis spectroscopy and photoluminescence (PL). XRD studies confirm the zinc blende phase of the nanocomposites and indicate the high purity of the samples. SEM studies indicate small nanoparticles clinging to the surface of a bigger particle. The Energy Dispersive Analysis by X‐rays (EDAX) spectrum reveals that the elemental composition of the nanocomposites consists primarily of Zn:S. FTIR studies indicate that the polymer matrix is closely associated with ZnS nanoparticles. The large number of hydroxyl groups in the polymer matrix facilitates the complexation of metal ions. The absorption spectra of the specimens show a blue shift in the absorption edge. The spectrum reveals an absorption edge at 320, 310 and 325 nm, respectively. PL of nanocomposites shows broad peaks in the violet–blue region (420–450 nm). The emission intensity changes with the nature of capping agent. The PL intensity of ZnS–HPMC nanocomposites is found to be highest among the studied nanocomposites. The results clearly indicate that hydroxyl‐functionalized HPMC is much more effective at nucleating and stabilizing colloidal ZnS nanoparticles in aqueous suspensions compared with PVA and starch. Copyright © 2015 John Wiley & Sons, Ltd.     

Blue excitable green emitting Ce3+ doped CaS phosphor for w‐LEDs

CaS:Ce³⁺ is an efficient green‐emitting (535 nm) phosphor, excitable with blue light (450–470 nm) and was synthesized via a solid‐state reaction method by heating under a reducing atmosphere. The luminescent properties, photoluminescent (PL) excitation and emission of the phosphor were analyzed by spectrofluorophotometry. The excitation and emission peaks of the CaS:Ce³⁺ phosphor lay in the visible region, which made them relevant for light‐emitting diode (LED) application for the generation of white light. Judd‐Oflet parameters were calculated and revealed that green light emitted upon blue illumination. The prepared phosphor had strong blue absorption at 470 nm and a broad green emission band range from 490–590 nm with the peak at 537 nm. The characteristics of the CaS:Ce³⁺ phosphor make it suitable for use as a wavelength tunable green emitting phosphor for three band white LEDs pumped by a blue LED (470 nm). The Commission International de l'Eclairage co‐ordinates were calculated by a spectrophotometric method using the spectral energy distribution (0.304, 0.526) and confirm the green emission. The potential application of this phosphor is as a phosphor‐converted white light‐emitting diode. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of ZnSe and ZnSe:Cu quantum dots by a room temperature photochemical (UV‐assisted) approach using Na2SeO3 as Se source and investigating optical properties

In this study, ZnSe and ZnSe:Cu quantum dots (QDs) were synthesized using Na₂SeO₃ as the Se source by a rapid and room temperature photochemical (UV‐assisted) approach. Thioglycolic acid (TGA) was employed as the capping agent and UV illumination activated the chemical reactions. Synthesized QDs were successfully characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) and UV–visible (UV–vis) spectroscopy, Fourier transform‐infrared (FT‐IR), and energy dispersive X‐ray spectroscopy (EDX). XRD analysis demonstrated the cubic zinc blend phase QDs. TEM images indicated that round‐shaped particles were formed, most of which had a diameter of about 4 nm. The band gap of the ZnSe QDs was higher than that for ZnSe in bulk. PL spectra indicated an emission with three peaks related to the excitonic, surface trap states and deep level (DL) states. The band gap and QD emission were tunable only by UV illumination time during synthesis. ZnSe:Cu showed green emission due to transition of electrons from the Conduction band (CB) or surface trap states to the ²T₂ acceptor levels of Cu²⁺. The emission was increased by increasing the Cu²⁺ ion concentration, such that the optimal value of PL intensity was obtained for the nominal mole ratio of Cu:Zn 1.5%.     

Microwave‐assisted sintering synthesis of greenish‐yellow emitting Sr2SiO4:Eu2+ phosphors

Europium ion (Eu²⁺) doped Sr₂SiO₄ phosphors with greenish‐yellow emission were synthesized using microwave‐assisted sintering. The phase structure and photoluminescence (PL) properties of the obtained phosphor samples were investigated. The PL excitation spectra of the Sr₂SiO₄:Eu²⁺ phosphors exhibited a broad band in the range of 260 nm to 485 nm with a maximum at 361 nm attributed to the 5f‐4d allowed transition of the Eu²⁺ ions. Under an excitation at 361 nm, the Sr₂SiO₄:Eu²⁺ phosphor exhibited a greenish‐yellow emission peak at 541 nm with an International‐Commission‐on‐Illumination (CIE) chromaticity of (0.3064, 0.4772). The results suggest that the microwave‐assisted sintering method is promising for the synthesis of phosphors owing to the decreased sintering time without the use of additional reductive agents.     

Luminescence studies on Al4B2O9:Eu2+ phosphor crystals

A novel blue‐emitting phosphor, Eu²⁺‐doping Al₄B₂O₉, was prepared via a modified solid‐state reaction. Al₄B₂O₉:Eu²⁺ nanoparticles with diameters varying in a range from 20 to 50 nm were obtained using urea as an auxiliary reagent at the optimum temperature of 850°C. The crystallization and particle sizes of Al₄B₂O₉:Eu²⁺ were investigated using powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Photoluminescence (PL) results showed that Al₄B₂O₉:Eu²⁺ phosphor could be efficiently excited by the ultraviolet region from 240 to 410 nm, exhibiting bright blue emission. Further investigation on concentration‐dependent emission spectra indicated that the Al_3.997B₂O₉:Eu²⁺_0.003 phosphor exhibited the strongest luminescent, and the relative PL intensity decreased with increasing Eu²⁺ concentration due to concentration quenching. In addition, the concentration quenching for the one‐Eu‐site emission centers was caused by the electric multipole–multipole interaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis,characterization, and photoluminescence property of Nd–TUD‐1

Here, five different samples of neodymium (Nd) incorporated 3D‐mesoporous siliceous materials were fabricated using a single‐step hydrothermal technique. Typically, all samples were subjected to several qualitative elemental and quantitative analyses such as X‐ray diffraction, N₂‐adsorption/desorption, scanning electron microscopy, energy dispersive X‐ray, mapping, high resolution transmission electron microscopy, diffuse reflectance ultraviolet–visible, and Raman spectroscopy. The characterization results showed that at small loading of Nd (i.e. Si/Nd < 20), only isolated centres of trivalent neodymium ions were tetrahedrally coordinated in the TUD‐1 matrix. However, with increasing neodymium loading, additional nanoparticles of neodymium oxide with size 10–20 nm were embedded into silica host pores. Detailed photoluminescence (PL) analysis of all samples was carried out by recording the emission profiles at two diverse excitation wavelengths, 333 and 343 nm, to understand the effect of the Nd³⁺ environment on the PL emission spectra with special attention to the area between 400 and 600 nm. Most importantly, different peaks of the emission spectrum of each sample exhibited a distinct shape based on the Nd³⁺ environment. This performance was superior evidence that PL can be applied as a simple and efficient characterization tool to understand the nature of Nd³⁺ ion linkage with a silica matrix.     

Novel red colour emitting Ca0.995Mg2(SO4)3:0.5Eu2+ phosphor under ultraviolet,blue, and green excitation for plant growth LEDs

In the recent few years, Eu²⁺- and Mn⁴⁺-activated phosphors are widely used as potential colour converters for indoor plant cultivation lighting application due to their marvellous luminescence characteristics as well as low cost. In this investigation, we synthesized novel red colour-emitting Ca_(2−x)Mg₂(SO₄)₃:xmol% Eu²⁺ (x = 0–1.0 mol%) phosphors via a solid-state reaction method in a reducing atmosphere. The photoluminescence (PL) excitation spectra of synthesized phosphors exhibited a broad excitation band with three excitation bands peaking at 349 nm, 494 nm, and 554 nm. Under these excitations, emission spectra exhibited a broad band in the red colour region at ~634 nm. The PL emission intensity was measured for different concentrations of Eu²⁺. The maximum Eu²⁺ doping concentration in the Ca₂Mg₂(SO₄)₃ host was observed for 0.5 mol%. According to Dexter theory, it was determined that dipole–dipole interaction was responsible for the concentration quenching. The luminous red colour emission of the sample was confirmed using Commission international de l'eclairage colour coordinates. The results of PL excitation and emission spectra of the prepared phosphors were well matched with excitation and emission wavelengths of phytochrome P_R. Therefore, from the entire investigation and obtained results it was concluded that the synthesized Ca_0.995Mg₂(SO₄)₃:0.5mol%Eu²⁺ phosphor has huge potential for plant cultivation application.     

Luminescence study of Dy or Ce activated LiCaBO3 phosphor for γ‐ray and C5+ ion beam irradiation

The photoluminescence and thermoluminescence characteristics of rare earths (Dy or Ce) activated LiCaBO₃ phosphors have been studied. Phosphors were synthesized by modified solid state synthesis. The phosphors were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and thermoluminescence (TL) for structural, morphological and luminescence studies. Dy³⁺ activated LiCaBO₃ shows emission at 486 and 577 nm due to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transition, respectively, whereas the PL emission spectra of Ce³⁺ activated LiCaBO₃ phosphor shows a broad band peaking at 432 nm, which is due to the transition from 5d level to the ground state of the Ce³⁺ ion. The thermoluminescence study was also carried out for both these phosphors for γ‐ray irradiation and carbon beam irradiation. Linearity was studied for a 0.4–3.1 Rad dose γ‐rays. Linear behaviour over this dose range was observed. Gamma ray‐irradiated phosphors were shown to be negligible fading upon storage. All the samples were also studied for 75 MeV C⁵⁺ ion beam exposure in the range of 3.75 × 10¹² – 7.5 × 10¹³ ion cm^–2 fluence. In addition to this, trapping parameters of all the samples were also calculated using Chen's peak shape method. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization and luminescence properties of CaMgSi2O6:Eu2+ blue phosphor

A blue CaMgSi₂O₆:Eu²⁺ phosphor was prepared by the solid‐state reaction method and the phosphor characterized in terms of crystal structure, particle size, photoluminescence (PL), thermoluminescence (TL) and mechanoluminescence (ML) properties using X‐ray diffraction (XRD), transmission electron microscopy (TEM), PL spectroscopy, TLD reader and ML impact technique. The XRD result shows that phosphor is formed in a single phase and has a monoclinic structure with the space group C2/c. Furthermore, the PL excitation spectra of Eu²⁺‐doped CaMgSi₂O₆ phosphor showed a strong band peak at 356 nm and the PL emission spectrum has a peak at 450 nm. The depths and frequency factors of trap centers were calculated using the TL glow curve by deconvolution method in which the trap depths were found to be 0.48 and 0.61 eV. The formation of CaMgSi₂O₆:Eu²⁺ phosphor was confirmed by Fourier transform infrared spectroscopy. The ML intensity increased linearly with the impact velocity of the piston used to deform the phosphor. It was shown that the local piezoelectricity‐induced electron bombardment model is responsible for the ML emission. Finally, the optical properties of CaMgSi₂O₆:Eu²⁺ phosphors are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Improvement of light emission of Mn-doped Zn(2) SiO(4) phosphors with sodium

Mn‐doped willemite (Zn₂SiO₄:Mn) green phosphor were synthesized by sol–gel technology. The effect of the addition of sodium, as in the composition Zn_{(1.92 – X)} Na_XMn_0.08SiO₄, on the emission behavior was studied. FT–IR and EPR results revealed that sodium ion is incorporated into the lattice and results in the formation of isolated Mn²⁺ and Mn–Mn pairs. The maximum emission intensity of the sample under ultraviolet (UV) excitation occurred at the sodium concentration of x = ~0.03. The green emission at about 525 nm is assigned to Mn²⁺–Mn²⁺ pair centres on nearest neighbour Zn sites. The highest intensity of the green emission for x = ~0.03 is well close to the highest concentration of the Mn²⁺–Mn²⁺ pair. Copyright © 2012 John Wiley & Sons, Ltd.