Role of Mn impurity in the deterioration of ZnS:Cu, Br electroluminescent phosphors

ZnS:Cu, Br powder EL phosphors showed 6-line EPR signal at 25°C whose intensity increases with Cu content and on annealing in Zn-vapour. The signal arises from native Mn impurity. The starting material does not show any EPR signal since Mn2+ acts as an affinity potential well for a hole in ZnS, forming Mn3+ - a chemically uncommon situation in sulfides. In doped ZnS, holes are trapped at Cu such that Mn2+ persists. Deterioration of EL brightness is accompanied by the decrease in EPR signal intensity due to field assisted hole transference to Mn2+. Intentional addition of Mn in ZnS:Cu, Br decreases the brightness and shortens life time. Stable phosphors require ZnS with Mn content less than 1014 cm−3.

Atomic Layer Deposition of Electroluminescent ZnS, SrS, and BaS Thin Films

The light emitted by flat panel displays (FPD) can be generated in many different ways, such as for example alternating current thin film electroluminescence (ACTFEL), liquid crystal display (LCD), light emitting diode (LED), or plasma display panel (PDP) technologies. In this work, the focus was on ACTFEL devices and the goal was to develop new thin film processes for light emitting materials in ACTFEL devices. The films were deposited with the atomic layer deposition (ALD) method, which has been utilized in the manufacturing of ACTFEL displays since the mid-1980s. The ALD method is based on surface-controlled self-terminated reactions and a maximum of one layer of the desired material can be prepared during one deposition cycle. Therefore, the film thickness can be controlled simply by adjusting the number of deposition cycles. In addition, both large areas and deep trench structures can be covered uniformly. During this work, new ALD processes were developed for the following thin film materials: BaS, CuxS, MnS, PbS, SrS, SrSe, SrTe, SrS1-xSex, ZnS, and ZnS1-xSex. In addition, several ACTFEL devices were prepared where the light emitting material was BaS, SrS, SrS1-xSex, ZnS, or ZnS1-xSex thin film that was doped with Ce, Cu, Eu, Mn, or Pb. The sulfoselenide films were made by substituting the elemental selenium for sulfur on the substrate surface during film deposition. In this way, it was possible to replace a maximum of 90% of the sulfur with selenium, and the XRD analyses indicated that the films were solid solutions. The polycrystalline BaS, SrS, and ZnS thin films were deposited at 180-400, 120-460, and 280-500 °C, respectively, and the processes had a wide temperature range where the growth rate of the films was independent of the deposition temperature. The electroluminescence studies showed that the doped sulfoselenide films resulted in low emission intensity. However, the emission intensities and emission colors of the doped SrS, BaS, and ZnS films were comparable with those found in earlier studies. It was also shown that the electro-optical properties of the different ZnS:Mn devices were different as a consequence of different ZnS:Mn processes. Finally, it was concluded that because the higher deposition temperature seemed to result in a higher emission intensity, the thermal stability of the reactants has a significant role when the light emitting materials of ACTFEL devices are deposited with the ALD method.

Synthesis of wurtzite-phase ZnS nanocrystal and its optical properties

The wurtzite phase of ZnS nanocrystal has been prepared by annealing in 200-600 degrees C temperature range, its cubic phase of 2-3 nm size. prepared through soft chemical method. Results of isochronal experiments of 2 h at different temperatures indicate that visible transformation to wurtzite from cubic ZnS appears at a temperature of 400 degrees C, which is about three times smaller than that of bulk ZnS phase transition temperature. The phases, nanostructures, and optical absorption characteristics are obtained through X-ray diffraction. transmission electron microscopy, and UV-visible absorption spectroscopy. A stable and green photoluminescence emission peaked at 518 nm is observed from the 600 degrees C annealed samples, under ultraviolet light excitation.

Highly Luminescent Mn-Doped ZnS Nanocrystals: Gram-Scale Synthesis

Following growth doping technique highly luminescent (quantum yield >50%) Mn-doped ZnS nanocrystals are synthesized via colloidal synthetictechnique. The dopant emission has been optimized with varying reaction parameters and found the ratio of Zn and S as well as the percentage of introduced dopant in the reaction mixture are key factors for controlling the intensity. The method is simple, hassle free, and can be scalable to gram level without hindering the quality of nanocrystals. These nanocrystals retain their emission during various ligand exchange processes and aqueous dispersion.

Hydrogel-assisted synthesis of nanotubes and nanorods of US, ZnS and CuS, showing some evidence for oriented attachment

By carrying out the reaction of appropriate metal compounds with Na2S in the presence of a tripodal cholamide-based hydrogel, nanotubes and nanorods of CdS, ZnS and CuS have been obtained. The nanostructures have been characterized by transmission electron microscopy and spectroscopic techniques. Evidence is presented for the assembly of short nanorods to form one-dimensional chains.

Biphenyl ethers conjugated CdSe/ZnS core/shell quantum dots and interpretation of the mechanism of amyloid fibril disruption

The biphenyl ethers (BPEs) are the potent inhibitors of TTR fibril formation and are efficient fibril disrupter. However, the mechanism by which the fibril disruption occurs is yet to be fully elucidated. To gain insight into the mechanism, we synthesized and used a new QD labeled BPE to track the process of fibril disruption. Our studies showed that the new BPE-QDs bind to the fiber uniformly and has affinity and specificity for TTR fiber and disrupted the pre-formed fiber at a relatively slow rate. Based on these studies we put forth the probable mechanism of fiber disruption by BPEs. Also, we show here that the BPE-QDs interact with high affinity to the amyloids of A beta(42), lysozyme and insulin. The potential of BPE-QDs in the detection of senile plaque in the brain of transgenic Alzheimer's mice has also been explored. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis and enhanced green photoluminescence emission from BCT ZnS nanocrystals

Body-centered-tetragonal (BCT) ZnS nanocrystals have been synthesized, for the first time to the best of our knowledge, by using the chemical coprecipitation method at higher synthesis temperatures of 65 and 95 degrees C. It is confirmed from X-ray diffraction (XRD) studies that in the high-temperature-synthesized samples, cubic and BCT phases coexist, in contrast to the room-temperature-synthesized sample, which consists of only cubic phase with sizes of the particles lying between 2 and 3 nm. The sizes of BCT phase nanocrystals are bigger than those of cubic phase of ZnS. The presence of BCT phase of ZnS in the samples is increased from 40 to 90% when the temperature of synthesis is increased from 65 to 95 degrees C. The nanocrystalline nature and UV-Vis absorption characteristics of the prepared samples have been studied with a transmission electron microscope (TEM) and a UV-Visible pectrophotometer, respectively. The room-temperature-synthesized ZnS sample shows photoluminescence (PL) emission in the blue region with multiple peaks, whereas the high-temperature-synthesized samples show PL emissions in the visible region. The Gaussian fittings of the measured PL spectra shows that three PL peaks at 429, 477, and 525 nm are appeared in the 65 degrees C sample and two peaks at 491 and 540 nm appear in the 95 degrees C sample with the enhanced PL intensity of the green peak at 540 nm. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Thermally Controlled Cyclic Insertion/Ejection of Dopant Ions and Reversible Zinc Blende/Wurtzite Phase Changes in ZnS Nanostructures

We report a reversible phase transformation of platelet-shaped ZnS nanostructures between wurtzite (WZ) and zinc blende (ZB) phases by reversible insertion/ ejection of dopant Mn(II) ions induced by a thermocyclic process. In a reaction flask loaded with WZ ZnS platelets and Mn molecular precursors, during heating Mn ions are incorporated and change the phase of the host nanostructures to ZB; during cooling Mn ions are spontaneously ejected, returning the host nanoplatelets to the original WZ phase. These reversible changes are monitored for several cycles with PL, EPR, XRD, and HRTEM. Interestingly, the (0001) WZ platelets transform to (110) ZB following a nucleation and growth process triggered by a local increase/depletion of the Mn2+ concentration in the nanocrystals.

Thermally Controlled Cyclic Insertion/Ejection of Dopant Ions and Reversible Zinc Blende/Wurtzite Phase Changes in ZnS Nanostructures

We report a reversible phase transformation of platelet-shaped ZnS nanostructures between wurtzite (WZ) and zinc blende (ZB) phases by reversible insertion/ ejection of dopant Mn(II) ions induced by a thermocyclic process. In a reaction flask loaded with WZ ZnS platelets and Mn molecular precursors, during heating Mn ions are incorporated and change the phase of the host nanostructures to ZB; during cooling Mn ions are spontaneously ejected, returning the host nanoplatelets to the original WZ phase. These reversible changes are monitored for several cycles with PL, EPR, XRD, and HRTEM. Interestingly, the (0001) WZ platelets transform to (110) ZB following a nucleation and growth process triggered by a local increase/depletion of the Mn2+ concentration in the nanocrystals.

Synthesis and photoluminescent properties of ZnS nanocrystals doped with copper and halogen

A novel wet-chemical precipitation method is optimized for the synthesis of ZnS nanocrystals doped with Cu+ and halogen. The nanoparticles were stabilized by capping with polyvinyl pyrrolidone (PVP). XRD studies show the phase singularity of ZnS particles having zinc-blende (cubic) structure. TEM as well as XRD line broadening indicate that the average crystallite size of undoped samples is similar to2 nm. The effects of change in stoichiometry and doping with Cu+ and halogen on the photoluminescence properties of ZnS nanophosphors have been investigated. Sulfur vacancy (Vs) related emission with peak maximum at 434 nm has been dominant in undoped ZnS nanoparticles. Unlike in the case of microcrystalline ZnS phosphor, incorporation of halogens in nanoparticles did not result V-Zn related self-activated emission. However, emission characteristics of nanophosphors have been changed with Cu+ activation due to energy transfer from vacancy centers to dopant centers. The use of halogen as co-activator helps to increase the solubility of Cu+ ions in ZnS lattice and also enhances the donor-acceptor type emission efficiency. With increase in Cu+ doping, Cu-Blue centers (CuZn-Cui+), which were dominant at low Cu+ concentrations, has been transformed into Cu-Green (Cu-Zn(-)) centers and the later is found to be situated near the surface regions of nanoparticles. From these studies we have shown that, by controlling the defect chemistry and suitable doping, photoluminescence emission tunability over a wide wavelength range, i.e., from 434 to 514 nm, can be achieved in ZnS nanophosphors. (C) 2003 Elsevier B.V. All rights reserved.

Onset of sphalerite to wurtzite transformation in ZnS nanoparticles

In this work, the incubation period for the onset of sphalerite to wurtzite transformation in isolated ZnS nanoparticles 2 to 7 nm in size was determined via the in situ isothermal annealing of as-synthesized sphalerite nanoparticles in a transmission electron microscope (TEM). Nanoparticles sitting on the TEM grid were well separated from each other in order to minimize particle sintering during the annealing operation. The phase transformation onset was observed at 300 degrees C, 350 degrees C, and 400 degrees C after 90, 10, and 4 min, respectively. These time-temperature data for the phase transformation onset were then used to calculate the activation energy for the nucleation of the wurtzite phase in 2 to 7 nm sphalerite particles. The activation energy determined was 24 Kcal/mol. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3622625]

Mechanical properties of ZnS nanowires and thin films: Microscopic origin of the dependence on size and growth direction

Mechanical properties of ZnS nanowires and thin films are studied as a function of size and growth direction using all-atom molecular dynamics simulations. Using the stress-strain relationship we extract Young's moduli of nanowires and thin films at room temperature. Our results show that Young's modulus of 0001] nanowires has strong size dependence. On the other hand, 01 (1) over bar0] nanowires do not exhibit a strong size dependence of Young's modulus in the size range we have investigated. We provide a microscopic understanding of this behavior on the basis of bond stretching and contraction due to the rearrangement of atoms in the surface layers. The ultimate tensile strengths of the nanowires do not show much size dependence. To investigate the mechanical behavior of ZnS in two dimensions, we calculate Young's modulus of thin films under tensile strain along the 0001] direction. Young's modulus of thin films converges to the bulk value more rapidly than that of the 0001] nanowire.

Room temperature synthesis of Mn2+ doped ZnS d-dots and observation of tunable dual emission: Effects of doping concentration, temperature, and ultraviolet light illumination

Mn2+ doped (0-50.0 molar %) ZnS d-dots have been synthesized in water medium by using an environment friendly low cost chemical technique. Tunable dual emission in UV and yellow-orange regions is achieved by tailoring the Mn2+ doping concentration in the host ZnS nanocrystal. The optimum doping concentration for achieving efficient photoluminescence (PL) emission is determined to be similar to 1.10 (at. %) corresponding to 40.0 (molar %) of Mn2+ doping concentration used during synthesis. The mechanism of charge transfer from the host to the dopant leading to the intensity modulated tunable (594-610 nm) yellow-orange PL emission is straightforwardly understood as no capping agent is used. The temperature dependent PL emission measurements are carried out, viz., in 1.10 at. % Mn2+ doped sample and the experimental results are explained by using a theoretical PL emission model. It is found that the ratio of non-radiative to radiative recombination rates is temperature dependent and this phenomenon has not been reported, so far, in Mn2+ doped ZnS system. The colour tuning of the emitted light from the samples are evident from the calculated chromaticity coordinates. UV light irradiation for 150 min in 40.0 (molar %) Mn2+ doped sample shows an enhancement of 33% in PL emission intensity. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4795779]

Effective Mass-Driven Structural Transition in a Mn-Doped ZnS Nanoplatelet

Mn doping in ZnS nanoplatelets has been shown to induce a structural transition from the wurtzite to the zinc blende phase. We trace the origin of this transition to quantum confinement effects, which shift the valence band maximum of the wurtzite and zinc blende polyrnorphs of ZnS at different rates as a function of the nanocrystal size, arising from different effective hole masses in the two structures. This modifies the covalency associated with Mn incorporation and is reflected in the size-dependent binding energy difference for the two structures.

Ultranarrow and Widely Tunable Mn2+-Induced Photoluminescence from Single Mn-Doped Nanocrystals of ZnS-CdS Alloys

Extensively studied Mn-doped semiconductor nanocrystals have invariably exhibited photoluminescence over a narrow energy window of width <= 150 meV in the orange-red region and a surprisingly large spectral width (>= 180 meV), contrary to its presumed atomic-like origin. Carrying out emission measurements on individual single nanocrystals and supported by ab initio calculations, we show that Mn PL emission, in fact, can (i) vary over a much wider range (similar to 370 meV) covering the deep green-deep red region and (ii) exhibit widths substantially lower (similar to 60-75 meV) than reported so far, opening newer application possibilities and requiring a fundamental shift in our perception of the emission from Mn-doped semiconductor nanocrystals.