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]

Investigations on doping induced changes in structural, electronic structure and magnetic behavior of spintronic Cr-ZnS nanoparticles

Dilute magnetic semiconducting Zn1-xCrxS (x = 0.00, 0.01, 0.03, 0.05, 0.07) nanoparticles were synthesized by the co-precipitation technique using thioglycerol as the capping agent. Powder X-ray diffraction studies showed that Zn1-xCrxS nanoparticles exhibit zinc blende structure with no secondary phase, indicating that Cr ions are substituted at the Zn sites. Photoluminescence and Raman studies show the incorporation of Cr in ZnS nanoparticles. X-ray absorption studies depict that the valence of Zn remains unchanged and maintained in the divalent state, upon doping with Cr. The M-H curves at room temperature indicate the presence of weak ferromagnetism at room temperature due to structural defects. The increase in ferromagnetism with increasing Cr content up to 3%, demonstrates the possibility of tailoring the weak ferromagnetism in ZnS by appropriate Cr doping. (C) 2015 Elsevier Ltd. All rights reserved.

Optical and magnetic properties of ZnS nanoparticles doped with Mn2+

ZnS:Mn nanoparticles of the cubic zinc blende structure with the average sizes of about 3 nm were synthesized using a coprecipitation method and their optical and magnetic properties were investigated. Two emission bands were observed in doped nanoparitcles and attributed to the defect-related emission of ZnS and the Mn2+ emission, respectively. With the increase of Mn2+ concentration, the luminescence intensities of these two emission bands increased and the ZnS emission band shifted to lower energy. Based on the luminescence excitation spectra of Mn2+, the 3d(5) level structure of Mn2+ in ZnS nanoparticles is similar to that in bulk ZnS:Mn, regardless of Mn2+ concentration. Magnetic measurements showed that all the samples exhibit paramagnetic behavior and no antiferromagnetic interaction between Mn2+ ions exists, which are in contrast to bulk ZnS:Mn. (c) 2005 Elsevier B.V. All rights reserved.

Photoluminescence of doped ZnS nanoparticles under hydrostatic pressure

The pressure dependence of the photoluminescence from ZnS : Mn2+, ZnS : Cu2+, and ZnS : Eu2+ nanoparticles were investigated under hydrostatic pressure up to 6 GPa at room temperature. Both the orange emission from the T-4(1) - (6)A(1) transition of Mn2+ ions and the blue emission from the DA pair transition in the ZnS host were observed in the Mn-doped samples. The measured pressure coefficients are -34.3(8) meV/GPa for the Mn-related emission and -3(3) meV/GPa for the DA band, respectively. The emission corresponding to the 4f(6)5d(1) - 4f(7) transition of Eu2+ ions and the emission related to the transition from the conduction band of ZnS to the t(2) level of Cu2+ ions were observed in the Eu- and Cu-doped samples, respectively. The pressure coefficient of the Eu-related emission was found to be 24.1(5) meV/GPa, while that of the Cu-related emission is 63.2(9) meV/GPa. The size dependence of the pressure coefficients for the Mn-related emission was also investigated. The Mn emission shifts to lower energies with increasing pressure and the shift rate (the absolute value of the pressure coefficient) is larger in the ZnS : Mn2+ nanoparticles than in bulk. Moreover, the absolute pressure coefficient increases with the decrease of the particle size. The pressure coefficients calculated based on the crystal field theory are in agreement with the experimental results. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absorption and luminescence of the surface states in ZnS nanoparticles

A broad absorption band around 500 nm is observed in ZnS nanoparticles. The absorption becomes more intensive and shifts to the blue as the particle size is decreased. The absorption energy is lower than the band gap of the particles and is considered to be caused by the surface states. This assignment is supported by the results of the fluorescence and of the thermoluminescence of the surface states. Both the absorption and the fluorescence reveal that the surface states are size dependent. The glow peak of the semiconductor particles is not varied as much upon decreasing size, indicating the trap depth of the surface states is not sensitive to the particle size. Considering these results, a new model on the size dependence of the surface states is proposed, which may explain our observations reasonably. (C) 1997 American Institute of Physics.

Thermoluminescence of ZnS nanoparticles

The thermoluminescence (TL) of ZnS nanoparticles is reported. The TL intensity increases as the particle size is decreased. The consistency of the size dependence of the TL with that of the surface fluorescence indicates that the TL may be related to the surface states. TL may be caused by the recombination of carriers released from the surface states or defect sites by heating. Smaller particles have higher surface/volume ratio and more surface states, therefore contain more accessible carriers for TL. Besides, the carrier recombination rate increases upon decreasing size due to the increase of the overlap between the electron and hole wave functions. These two effects may make the TL increase upon decreasing size of the particles. The appearance of TL prior to any radiation reveals that trapped carriers have pre-existed. The investigation of TL may provide some useful information about the surface states that may explain the size dependence of the surface fluorescence. (C) 1997 American Institute of Physics.

Synthesis of wurtzite ZnS nanoparticles using the microwave assisted solvothermal method

In this article, we report the development of an efficient and rapid microwave assisted solvothermal (MAS) method to prepare wurtzite ZnS nanoparticles at 413 K using different precursors. The materials obtained were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (MET) ultraviolet-visible (UV-vis) and photoluminescence (PL) measurements. The structure, surface chemical composition and optical properties were investigated as a function of the precursor. In addition, effects as well as merits of microwave heating on the processing and characteristics of ZnS nanoparticles obtained are reported. The possible formation mechanism and optical properties of these nanoparticles were also reported. © 2012 Elsevier B.V. All rights reserved.

Zinc blende versus wurtzite ZnS nanoparticles: control of the phase and optical properties by tetrabutylammonium hydroxide

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigation of phtoluminesecence under hydrostatic pressure in different sized ZnS : Mn nanoparticles

The PL spectra for the 10, 4. 5, 3. 5, 3, 1 nm sized ZnS:Mn2+ nanoparticles and corresponding bulk material under different pressures were investigated. The orange emission band originated from the T-4(1)-(6)A(1) transition of Mn2+ ions showed obvious red shift with the increasing of pressures. The pressure coefficients of Mn-related emissions measured from bulk, 10, 4. 5, 3.5 and 3 nm samples are -29.4 +/- 0.3, -30.1 +/- 0.3, -33.3 +/- 0.6, -34.6 +/- 0.8 and -39 +/- 1 meV/GPa, respectively. The absolute value of the pressure coefficient increases with the decrease of the size of particles. The size dependence of crystal field strength Dq and Racah parameter B accounts for the size behavior of the Mn-related emission in ZnS:Mn nanoparticles. The pressure behavior of Mn-related emission in the 1 nm sized sample is somewhat different from that of other nanoparticles. It may be due to smaller size of 1 nm sample and the special surface condition since ZnS nanoparticles are formed in the cavities of ziolite-Y for the 1 nm sample.

Synthesis and photoluminescence of ZnS : Cu nanoparticles

The room-temperature photoluminescence (PL) of copper doped zinc sulfide (ZnS:Cu) nanoparticles were investigated. These ZnS:Cu nanoparticles were synthesized by a facile wet chemical method, with the copper concentration varying from 0 to 2 mol%. By Gaussian fitting, the PL spectrum of the undoped ZnS nanoparticles was deconvoluted into two blue luminescence peaks (centered at 411 nm and 455 nm, respectively), which both can be attributed to the recombination of the defect sates of ZnS. But for the doped samples, a third peak at about 500 nm was also identified. This green luminescence originates from the recombination between the shallow donor level (sulfur vacancy) and the t(2) level of Cu2+. With the increase of the CU2+ concentration, the green emission peak is systematically shifted to longer wavelength. In addition, it was found that the overall photoluminescence intensity is decreased at the Cu2+ concentration of 2%. The concentration quenching of the luminescence may be caused by the formation of CuS compound. (c) 2005 Elsevier B.V. All rights reserved.

Energy structure and fluorescence of Eu2+ in ZnS : Eu nanoparticles

Eu2+-doped ZnS nanoparticles with an average size of around 3 nm were prepared, and an emission band around 530 nm was observed. By heating in air at 150 degrees C, this emission decreased, while the typical sharp line emission of Eu3+ increased. This suggests that the emission around 530 nm is from intraion transition of Eu2+: In bulk ZnS:Eu2+, no intraion transition of Eu2+ was observed because the excited states of Eu2+ are degenerate with the continuum of the ZnS conduction band. We show that the band gap in ZnS:Eu2+ nanoparticles opens up due to quantum confinement, such that the conduction band of ZnS is higher than the first excited state of Eu2+, thus enabling the intraion transition of Eu2+ to occur.

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.

Observation of Combined Effect of Temperature and Pressure on Cubic to Hexagonal Phase Transformation in ZnS at the Nanoscale

The temperature of allotropic phase transformation in ZnS (cubic to wurtzite) changes with pressure and particle size. In this paper we have explored the interrelation among these through a detailed study of ZnS powders obtained by a temperature-controlled high energy milling process. By employing the combined effect of temperature and pressure in an indigenously built cryomill, we have demonstrated a large-scale, low-temperature synthesis of wurtzite ZnS nanoparticles. The synthesized products have been characterized for their phase and microstructure by the use of X-ray diffraction and transmission electron microscopic techniques. Further, it has been demonstrated that the synthesized materials exhibit photoluminescence emissions in the UV-visible region with an unusual doublet pattern due to the presence of both cubic and hexagonal wurtzite domains in the same particles. By further fine-tuning the processing conditions, it may be possible to achieve controlled defect related photoluminescence emissions from the ZnS nanoparticles.

Photoluminescence properties of Eu3+-doped ZnS nanocrystals prepared in a water/methanol solution

Monodispersed ZnS and Eu3+-doped ZnS nanocrystals have been prepared through the co-precipitation reaction of inorganic precursors ZnCl2, EuCl3, and Na2S in a water/methanol binary solution. The mean particle sizes are about 3-5 nm. The structures of the as-prepared ZnS nanoparticles are cubic (zinc blende) as demonstrated by an x-ray powder diffraction. Photoluminescence studies showed a stable room temperature emission in the visible spectrum region for all the samples, with a broadening in the emission band and, in particular, a partially overlapped twin peak in the Eu3+-doped ZnS nanocrystals. The experimental results also indicated that Eu3+-doped ZnS nanocrystals, prepared by controlling synthetic conditions, were stable. (C) 2002 American Institute of Physics.