Study of size dependent photoluminescence properties of copper doped sodium hexametaphosphate capped ZnS nanoparticles

Copper doped ZnS nanoparticles stabilized by sodium hexametaphosphate (SHMP) have been prepared via the wet chemical method using thiourea and sodium sulphide as chalcogenide sources. The XRD pattern showed that ZnS nanoparticles had zinc blende structure and line broadening suggests the formation of an amorphous compound. Absorption measurements were done for three different concentrations of dopant concentrations. The PL spectrum for the sample synthesized using Na₂S·9H₂O showed a sharp emission peak around 510 nm with full width at half maximum (FWHM)<10 nm. The role of the capping agent and sulphide source on optical properties of as synthesized nanoparticles by steady-state photoluminescence (PL) spectroscopy has been studied.     

Effect of impurity concentration on optical and magnetic properties in ZnS:Cu nanoparticles

To obtain enhanced room temperature ferromagnetism (RTFM) along with the increase in optical bandgap in the compound semiconductors has been an interesting topic. Here, we report RTFM along with increase in energy bandgap in chemically synthesized Zn_1−xCu_xS (0 ≤ x ≤ 0.04) DMS nanoparticles. Structural properties of the synthesized samples studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show the formation of cubic phase Cu doped ZnS nanoparticles of ~3–5 nm size. An intrinsic weak ferromagnetic behavior was observed in pure ZnS sample (at 300 K) which got increased in Cu doped samples and was understood due to defect induced ferromagnetism. UV–vis measurement showed increase in the energy bandgap with the increase in Cu doping. The PL study suggested the presence of sulfur and zinc vacancies and surface defects which were understood contributing to the intrinsic FM behavior.     

Simultaneous ultrasound-assisted removal of sunset yellow and erythrosine by ZnS:Ni nanoparticles loaded on activated carbon: Optimization by central composite design

The present study focused on the simultaneous ultrasound-assisted removal of sunset yellow and erythrosine dyes from aqueous solutions using ZnS:Ni nanoparticles loaded on activated carbon (ZnS:Ni-NP-AC) as an adsorbent. ZnS:Ni nanoparticles were synthesized and characterized using different techniques such as FESEM, XRD and TEM. The effects of various parameters such as sonication time, pH, initial dye concentrations and adsorbent dose on the percentage of dye removal were investigated. Parameters were optimized by central composite design (CCD) combined with response surface methodology (RSM) and desirability function (DF). A good agreement between experimental and predicted values was observed. The ultrasound-assisted adsorbent (0.04 g) was capable of high percentage removal (98.7% and 99.6%) of sunset yellow and erythrosine in short time (3.8 min).     

Emission characteristics of SPAN-80 activated ZnS nanocolloids

Quantum surface effects (new emission bands, blueshifts, intensity enhancement) were observed in SPAN-80 activated ZnS nanocolloids and explained in terms of time-dependent density functional theory. The experimental evidences were demonstrated for both undoped and Cu, Mn-doped colloidal phases. The photoluminescence spectra of these materials showed a new green band at 520 nm (ZnS:Cu) and a yellow-orange band at 576 nm (ZnS:Mn) besides a blue band at 465 nm. All bands lie in the visible region and are blueshifted, show sharp emissions with narrow widths and have approximately 20-times stronger intensities in comparison with those of the bulk samples. The time-resolved luminescence spectra showed that the life-times of free electrons were 0.12 μs and 1.9 ms in ZnS:Cu and ZnS:Mn correspondingly.     

Emission of Cu-related complexes in ZnO:Cu nanocrystals

Photoluminescence (PL), its temperature dependence, scanning electronic microscopy (SEM) and X ray diffraction (XRD) have been applied for the comparative study of varying the emission, morphology and crystal structure of ZnO and ZnO:Cu nanocrystals (NCs) versus technological routines, as well as the dependence of ZnO:Cu NC parameters on the Cu concentration. A set of ZnO and ZnO Cu NCs was prepared by the electrochemical (anodization) method at a permanent voltage and different etching durations with follows thermal annealing at 400 °C for 2 h in ambient air. The size of ZnO NCs decreases from 300 nm×540 nm down to 200 nm×320 nm with etching duration increasing. XRD study has confirmed that thermal annealing stimulates the ZnO oxidation and crystallization with the formation of wurtzite ZnO crystal lattice. XRD method has been used for monitoring the lattice parameters and for confirming the Cu doping of ZnO Cu NCs. In ZnO Cu NCs four defect related PL bands are detected with the PL peaks at 1.95–2.00 eV (A), 2.15-2.23  eV (B), 2.43–2.50 eV (C) and 2.61–2.69 eV (D). Highest PL intensities of orange, yellow and green emissions have been obtained in ZnO Cu NCs with the Cu concentration of 2.28 at%. At Cu concentration increasing (≥2.28 at%) the PL intensities of the bands A, B, C decrease and the new PL band peaked at 2.61–2.69 eV at 10 K appears in the PL spectrum. The variation of PL intensities for all PL bands versus temperature has been studied and the corresponding activation energies of PL thermal decay have been estimated. The type of Cu-related complexes is discussed using the correlation between the PL spectrum transformation and the variation of XRD parameters in ZnO Cu NCs.     

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.     

Synthesis and characterization of ZnS:Ni-NPs loaded on AC derived from apple tree wood and their applicability for the ultrasound assisted comparative adsorption of cationic dyes based on the experimental design

The applicability of ZnS:Ni nanoparticles loaded on activated carbon derived from apple tree wood (ZnS:Ni-NPs-ACATW) for the adsorption of Methylene Blue (MB) and Janus Green B (JGB) dyes in single system from water solution has been described. The synthesized adsorbent characterized and identified by UV–Vis, FE-SEM, EDX, TEM, FTIR and XRD. The influences of operation parameters including initial MB or JGB concentration (9.0–33.0 mg L⁻¹), pH (4.0–10.0), extent of adsorbent (0.08–0.12 g) and sonication time (4.0–8.0 min) investigated and subsequently best operational condition optimized by central composite design (CCD) combined with response surface methodology (RSM) and desirability function (DF) using STATISTICA 10.0 software. At optimum conditions, maximum MB and JSB adsorption onto ZnS:Ni-NPs-ACATW, i.e. 99.57% ± 1.34 and 98.70% ± 2.01, respectively was achieved pH of 7.0, 0.11 g adsorbent, 14 and 28 mg L⁻¹ of MB and JSB concentration respectively and 8 min sonication time. Experimental data were modelled by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) isotherms. Langmuir isotherm and monolayer adsorption capacity of MB and JSB was found to be 21.79 and 28.01 mg g⁻¹ respectively. The regression results strongly support more contribution of pseudo-second-order model for more accurate and repeatable representation of kinetic data. These results reveal that ZnS:Ni-NPs-ACATW could be useful as agents to efficiently remove dyes (JGB and MB) from contaminated water and can be very well recommended for wastewater remediation and control of environmental pollution.     

Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media

3-Mercaptopropionic acid-capped core/shell ZnS:Cu/ZnS and ZnS:Mn/ZnS doped quantum dots (QDs) prepared through hydrothermal methods exhibit high photoluminescence intensity as well as good photostability. These water-dispersible nanoparticles exhibit high fluorescence sensitivity to folic acid due to the high affinity of the carboxylate groups and nitrogen atoms of folic acid towards the Zn surface atoms of the doped dots. Quenching of the fluorescence intensity of the QDs allows the detection of folic acid concentrations as low as 11 μM, thus affording a very sensitive system for the sensing of this biologically active molecule in aqueous solution. The possible quenching mechanism is discussed.     

The study of structure and optoelectronic properties of ZnS and ZnO films on porous silicon substrates

ZnS and ZnO films were prepared on porous silicon (PS) substrates with the same porosity by pulsed laser deposition (PLD), and the structural, optical and electrical properties of ZnS and ZnO films on PS were investigated at room temperature by X-ray diffraction (XRD), scanning electron microscope (SEM), optical absorption measurement, photoluminescence (PL) and I–V characteristic studies. The prepared ZnS was obtained in the cubic phase along β-ZnS (1 1 1) orientation which showed a perfect match with the earlier report while ZnO films were obtained in c-axis orientation. There appeared some cracks in the surface of ZnS and ZnO films due to the roughness of PS substrates. Luminescence studies of ZnS/PS and ZnO/PS composites indicated room temperature emission in a broad, intense, visible photoluminescence band, which cover the blue emission to red emission, exhibiting intensively white light emission. Based on the I–V characteristic, ZnS/PS heterojunction exhibited the rectifying junction behavior, while the I–V characteristic of ZnO/PS heterostructure was different from that of the common diode, whose reverse current was not saturated.     

Two and four photon absorption and nonlinear refraction in undoped,chromium doped and copper doped ZnS quantum dots

The ZnS quantum dots (QDs) with Cr and Cu doping were synthesized by chemical co-precipitation method. The nanostructures of the prepared undoped and doped ZnS QDs were characterized by UV–vis spectroscopy, Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The sizes of QDs were found to be within 3–5 nm range. The nonlinear parameters viz. Two photon absorption coefficient (β₂), nonlinear refractive index (n₂), third order nonlinear susceptibility (χ³) at wavelength 532 nm and Four photon absorption coefficient (β₄) at wavelength 1064 nm have been calculated by Z-scan technique using nanosecond Nd:YAG laser in undoped, Cr doped and Cu doped ZnS QDs. Higher values of nonlinear parameters for doped ZnS infer that they are potential material for the development of photonics devices and sensor protection applications.     

Effect of Ce and Cu co-doping on the structural,morphological, and optical properties of ZnO nanocrystals and first principle investigation of their stability and magnetic properties

Ce, Cu co-doped ZnO (Zn_1−2xCe_xCu_xO: x=0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) nanocrystals were synthesized by a microwave combustion method. These nanocrystals were investigated by using X-ray diffraction (XRD), UV–visible diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The stability and magnetic properties of Ce and Cu co-doped ZnO were probed by first principle calculations. XRD results revealed that all the compositions are single crystalline. hexagonal wurtzite structure. The optical band gap of pure ZnO was found to be 3.22 eV, and it decreased from 3.15 to 3.10 eV with an increase in the concentration of Cu and Ce content. The morphologies of Ce and Cu co-doped ZnO samples confirmed the formation of nanocrystals with an average grain size ranging from 70 to 150 nm. The magnetization measurement results affirmed the antiferro and ferromagnetic state for Ce and Cu co-doped ZnO samples and this is in agreement with the first principles theoretical calculations.     

Synthesis and surface modification of ZnO:Cu nanoparticles by silica and PMMA

ZnO nanoparticles doped with Cu were synthesized by solid state reaction using different precursor routes and varying growth environment. Average crystallite size varied from 40 to 100 nm depending upon synthesis temperature, lower temperature favouring smaller particle size. Scanning electron microscope (SEM) images showed that particles synthesized at 250 °C were in the shape of nanorods but those synthesized at 900 °C had spherical shape. Luminescence emission showed marked dependence on the growth conditions varying from ultraviolet (UV) emission to green emission. For making the luminescent nanoparticles bio-compatible, a bioinorganic interface on ZnO:Cu nanoparticles was created by coating them with inert silica. Surface modification of ZnO:Cu was also done with lipophilic polymethylmethacrylate (PMMA). ZnO:Cu nanoparticles showed hexagonal wurtzite structure and the coating of silica was confirmed with the presence of two extra peaks due to silica in the XRD spectra. Thermogravimetric analysis (TGA) and FTIR spectroscopy indicated that PMMA molecules were adsorbed on the surface of ZnO:Cu nanoparticles. SEM images revealed that PMMA adsorption improved the dispersibilty of ZnO:Cu nanoparticles.     

Nanostructure materials for destruction of warfare agents and eco-toxins prepared by homogeneous hydrolysis with thioacetamide: Part 1—zinc oxide

Zinc sulphide (ZnS) nanoparticles were prepared by homogeneous hydrolysis of zinc sulphate and thioacetamide (TAA) at 80 °C. After annealing at temperature above 400 °C in oxygen atmosphere, zinc oxide (ZnO) nanoparticles were obtained. The ZnS and ZnO nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission microscopy (HRTEM), selected area electron diffraction (SAED), by BET and BJH methods used for surface area and porosity determination. The photocatalytic activity of the as-prepared ZnO samples was determined by the decomposition of Orange II in the aqueous solution under UV irradiation of 365 nm of wavelength.     

Physical reasons of emission transformation in infrared CdSeTe/ZnS quantum dots at bioconjugation

The core/shell CdSeTe/ZnS quantum dots (QDs) with emission at 780–800 nm (1.55–1.60 eV) have been studied by means of photoluminescence (PL) and Raman scattering methods in the nonconjugated state and after conjugation to different antibodies (Ab): (i) mouse monoclonal [8C9] human papilloma virus Ab, anti-HPV 16-E7 Ab, (ii) mouse monoclonal [C1P5] human papilloma virus HPV16 E6+HPV18 E6 Ab, and (iii) pseudo rabies virus (PRV) Ab. The transformations of PL and Raman scattering spectra of QDs, stimulated by conjugated antibodies, have been revealed and discussed.The energy band diagram of core/shell CdSeTe/ZnS QDs has been designed that helps to analyze the PL spectra and their transformations at the bioconjugation. It is shown that the core in CdSeTe/ZnS QDs is complex and including the type II quantum well. The last fact permits to explain the nature of infrared (IR) optical transitions (1.55–1.60 eV) and the high energy PL band (1.88–1.94 eV) in the nonconjugated and bioconjugated QDs. A set of physical reasons has been analyzed with the aim to explain the transformation of PL spectra in bioconjugated QDs. Finally it is shown that two factors are responsible for the PL spectrum transformation at bioconjugation to charged antibodies: (i) the change of energy band profile in QDs and (ii) the shift of QD energy levels in the strong quantum confinement case. The effect of PL spectrum transformation is useful for the study of QD bioconjugation to specific antibodies and can be a powerful technique for early medical diagnostics.     

Re-charging the luminescence states in CdSe/ZnS quantum dots at the conjugation to Osteopontin antibodies

The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.     

Synthesis, structural and optical characterization of nanocrystalline ZnS:Cu embedded in silica matrix

The synthesis of Cu doped ZnS nanoparticles inside the pore of an inorganic silica gel matrix is presented. The synthesized nanoparticles were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). X-ray diffraction pattern reveals the crystalline wurtzite phase of ZnS. The existence of silica gel in modeling morphologies of the nanoparticles was characterized using Fourier transform infrared (FTIR) spectrometer. Thickness of the silica shell was also calculated. UV- absorption spectrum shows the appearance of an absorption peak at 273 nm which confirms the blue shift as compared to that of bulk ZnS. The photoluminescence (PL) emission spectrum of the sample showed a broad band in the range 465-510 nm due to the transition from the conduction band edge of ZnS nanocrystals to the acceptor like t₂ state of Cu.     

Laser diode end-pumped passively Q-switched Tm,Ho:YLF laser with Cr:ZnS as a saturable absorber

Output performance of a continuous-wave (CW) laser diode end-pumped passively Q-switched Tm,Ho:YLF laser is demonstrated with a Cr:ZnS crystal as the saturable absorber. We particularly investigate the influence of saturable absorber's position in the resonator when the Cr:ZnS crystal is placed close to and far from the laser beam waist. We compare the experimental results at the two different positions, and find that the laser shows unusual output characteristics when the Cr:ZnS saturable absorber is placed close to the beam waist. The pulse width and the pulse energy almost keep constant, measured about 1.25 μs and 4 μJ respectively, when the pump power is changed in the range of 1–1.9 W. Moreover, the pulse repetition frequency can be tuned between 1.3 kHz and 2.6 kHz by changing the pump power. The output wavelength of the passively Q-switched laser shifts to 2053 nm from 2067 nm in CW operation.     

Structural and optical characterization of ZnS nanoparticles co-doped with Mn and Te

Nanoparticles of Zinc sulfide co-doped with equal atomic percentages of Mn and Te (5, 10 and 15 at%) were synthesized for the first time by chemical co-precipitation method. Thiophenol was used to passivate the surface of the particles. The as-prepared samples were amorphous in nature and nano-crystallinity was induced after calcining at 300 °C/2 h. The nanoparticles were characterized by EDAX, XRD, TEM, optical absorption and PL studies. EDAX spectra revealed only minor deviations of the dopant concentrations from the target compositions. The nanoparticles showed cubic structure. The particle size estimated from XRD/TEM was in the range 3–5 nm. Optical absorption studies showed a blue-shift of the fundamental absorption edge with respect to that of bulk ZnS. PL spectra showed emission in the red region with composition dependent emission wavelength. ZnS nanoparticles doped with Mn (5 and 10 at%) were also synthesized and characterized for comparison.     

Preparation, characterization and study of optical properties of ZnS nanophosphor

In this work the preparation, characterization and photoluminescence studies of pure and copper-doped ZnS nanophosphors are reported, which are prepared by using solid-state reaction technique at a temperature of 100 °C. The as-obtained samples were characterized by X-ray diffraction (XRD) and UV-VIS Reflectance spectroscopy. The XRD analysis confirms the formation of cubic phase of undoped as well as Cu²⁺-doped ZnS nanoparticles. Furthermore it shows that the average size of pure as well as copper-doped samples ranges from 15 to 50 nm. The room-temperature PL spectra of the undoped ZnS sample showed two main peaks centered at around 421 and 450 nm, which are the characteristic emissions of interstitial zinc and sulfur vacancies, respectively. The PL of the doped sample showed a broad-band emission spectrum centered at 465 nm accompanied with shoulders at around 425, 450 and 510 nm, which are the characteristic emission peaks of interstitial zinc, sulfur vacancies and Cu²⁺ ions, respectively. Our experimental results indicate that the PL spectrum confirms the presence of Cu²⁺ ions in the ZnS nanoparticles as expected.     

Preserving long-term emission stability of carbon nanotube field emitter using aluminum layer

Carbon nanotube (CNT) field emitter was fabricated, and then its emission stability was evaluated with three different anode structures; indium tin oxide (ITO)/glass, ZnS:Cu,Al(green phosphor)/ITO/glass, and Al/ZnS:Cu,Al/ITO/glass. It was found that the electron emission from CNTs to the phosphor layer degrades much faster than the emission to ITO layer does. The current decay time from 100 μA/cm² to 50 μA/cm² for ITO/glass and ZnS:Cu,Al/ITO/glass were 250 h and 20 h, respectively. Such rapid decay in emission current with the phosphor-coated anode was found to be attributed to the formation of Zn particles on CNTs during the field emission. However, the deposition of aluminum layer on the phosphor, in other words, using the anode structure of Al/ZnS:Cu,Al/ITO/glass recovered the stability that is comparable to that with an ITO/glass. The aluminum layer was found to efficiently prevent phosphor elements from being degassed, preserving the long-term emission stability of carbon nanotubes.