Synthesis and luminescence of ZnMgS : Mn2+ nanoparticles

Efficient green emission from ZnMgS:Mn2+ nanoparticles prepared by co-doping Mg2+ and Mn2+ ions into ZnS lattices has been observed. The synthesis is carried out in aqueous solution, followed by a post-annealing process, thus showing the features of less complexity, low cost, and easy incorporation of dopants. In comparison with the emission of ZnS:Mn2+ nanoparticles, which is located generally around 590 nm, the photoluminescence of ZnMgS:Mn2+ nanoparticles is blue-shifted by 14 nm in wavelength, leading to the enhanced green emission. The X-ray diffraction, electron spin resonance, and pressure dependent photoluminescence measurements suggest that the change of the crystal field caused by Mg2+ ionic doping and the lower symmetry in the nanoparticles may account for the blue-shift of the photoluminescence. The ZnMgS:Mn2+ nanoparticles with 1% Mn2+ doping exhibit the strongest luminescence, which could potentially meet the requirements for the construction of green light emitting diodes.

Temperature and pressure dependences of the Mn2+ and donor-acceptor emissions in ZnS : Mn2+ nanoparticles

Temperature and pressure dependent measurements have been performed on 3.5 nm ZnS:Mn2+ nanoparticles. As temperature increases, the donor-acceptor (DA) emission of ZnS:Mn2+ nanoparticles at 440 nm shifts to longer wavelengths while the Mn2+ emission (T-4(1)-(6)A(1)) shifts to shorter wavelengths. Both the DA and Mn2+ emission intensities decrease with temperature with the intensity decrease of the DA emission being much more pronounced. The intensity decreases are fit well with the theory of thermal quenching. As pressure increases, the Mn2+ emission shifts to longer wavelengths while the DA emission wavelength remains almost constant. The pressure coefficient of the DA emission in ZnS:Mn2+ nanoparticles is approximately -3.2 meV/GPa, which is significantly smaller than that measured for bulk materials. The relatively weak pressure dependence of the DA emission is attributed to the increase of the binding energies and the localization of the defect wave functions in nanoparticles. The pressure coefficient of Mn2+ emission in ZnS:Mn2+ nanoparticles is roughly -34.3 meV/GPa, consistent with crystal field theory. The results indicate that the energy transfer from the ZnS host to Mn2+ ions is mainly from the recombination of carriers localized at Mn2+ ions. (C) 2002 American Institute of Physics.

Pressure dependence of Mn2+ fluorescence in ZnS : Mn2+ nanoparticles

The photoluminescence of Mn2+ in ZnS:Mn2+ nanoparticles with an average size of 4.5 nm has been measured under hydrostatic pressure from 0 to 6 GPa. The emission position is red-shifted at a rate of -33.3+/-0.6meV/GPa, which is in good agreement with the calculated value of -30.4meV/GPa using the crystal field theory. (C) 2000 Elsevier Science B.V. All rights reserved.

Pressure dependence of Mn2+ luminescence in differently sized ZnS : Mn nanoparticles

The pressure behavior of Mn2+ emission in the 10-, 4.5-, 3.5-, 3-, and 1-nm-sized ZnS:Mn2+ nanoparticles is investigated. The 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. The pressure coefficient increases with the decrease in particle size with the 1-nm-sized particles as an exception. Pressure coefficient calculations based on the crystal field theory are in agreement with the experimental results. The pressure dependence of the emission intensity is also size dependent. For nanoparticles 1 and 3 nm in size, the luminescence intensity of Mn2+ decreases dramatically with increasing pressure, while, for bulk and particles with average sizes of 3.5, 4.5, and 10 nm, the luminescence intensity of Mn2+ is virtually unchanged at different pressures. The bandwidth increases faster with increasing pressure for smaller particles. This is perhaps due to the fact that there are more Mn2+ ions at the near-surface sites and because the phonon frequency is greater for smaller particles. These new phenomena provide some insight into the luminescence behavior of Mn2+ in ZnS:Mn2+ nanoparticles.

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.

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.

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.

Surface states induced photoluminescence from Mn2+ doped CdS nanoparticles

Manganese doped CdS nanoparticles were synthesized in basic aqueous solution by using mercapto acetate as capping reagents. The nanoparticles were characterized by HRTEM, EPR, photoluminescence and optical absorption measurements. Out of our expectation, doping of Mn2+ ions altered the recombination paths in CdS nanoparticles markedly. The surface stares facilitated PL from Mn2+ doped CdS nanoparticles is reported. A complete suppression of the emission from surface states at room temperature when doping with Mn2+ ions has been observed for the first time. (C) 2000 Elsevier Science Ltd. All rights reserved.

Temperature behaviour of the orange and blue emissions in ZnS : Mn nanoparticles

The temperature dependences of the orange and blue emissions in 10, 4.5, and 3 nm ZnS:Mn nanoparticles were investigated. The orange emission is from the T-4(1)-(6)A(1) transition of Mn2+ ions and the blue emission is related to the donor-acceptor recombination in the ZnS host. With increasing temperature, the blue emission has a red-shift. On the other hand, the peak energy of the orange emission is only weakly dependent on temperature. The luminescence intensity of the orange emission decreases rapidly from 110 to 300 K for the 10 nm sample but increases obviously for the 3 nm sample, whereas the emission intensity is nearly, independent of temperature for the 4.5 nm sample. A thermally activated carrier-transfer model has been proposed to explain the observed abnormal temperature behaviour of the orange emission in ZnS:Mn nanoparticles.

Electrospinning Synthesis and Luminescence Properties of One-Dimensional Zn2SiO4:Mn2+ Microtibers and Microbelts

One-dimensional Mn2+-doped Zn2SiO4 rnicrobelts and microfibers were prepared by a simple and cost-effective electrospinning process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The XRD and DTA results show that the Zn2SiO4 phase begins to crystallize at 800 degrees C and crystallizes completely around 1000 degrees C. SEM results indicate that the as-prepared microbelts/fibers are smooth, whose diameters decrease with increasing the annealing temperature. The average diameter of the Zn2SiO4:Mn2+ microfibers annealed at 1000 degrees C is 0.32 mu m, and their lengths reach up to several millimeters. The average width and thickness of the Zn2SiO4:Mn2+ microbelts fired at 1000 degrees C are around 0.48 and 0.24 mu m, respectively.

Synthesis and characterization of high-quality ZnS, ZnS : Mn2+, and ZnS : Mn2+/ZnS (core/shell) luminescent nanocrystals

High-quality ZnS, ZnS:Mn2+, and ZnS:Mn2+/ZnS (core/shell) nanocrystals (NCs) were synthesized via a high-boiling solvent process and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectra. The monodisperse ZnS NCs (size = 8 nm), which self-assembled into several micrometer-sized domains, were achieved by adopting poly(ethylene glycol) (PEG) in the reaction process (without using a size-selection process). The obtained ZnS:Mn2+ and ZnS:Mn2+/ZnS core/shell NCs are highly crystalline and quasimonodisperse with an average particle size of 6.1 and 8.4 nm, respectively. All of the as-formed NCs can be well dispersed in hexane to form stable and clear colloidal solutions, which show strong visible emission (blue for ZnS and red-orange for ZnS:Mn2+ and ZnS:Mn2+/ZnS) under UV excitation. The growth of a ZnS shell on ZnS:Mn2+ NCs, that is, the formation of ZnS:Mn2+/ZnS core/shell NCs, resulted in a 30% enhancement in the PL intensity with respect to that of bare ZnS:Mn2+ NCs due to the elimination of the surface defects.

Tailoring The Mechanical Performance Of Epoxy Resin By Various Nanoparticles

Flexible organic elastomeric nanoparticles (ENP) and two kinds of rigid inorganic silica nanoparticles were dispersed respectively into a bisphenol-A epoxy resin in order to tailor and compare the performance of mechanical properties. It was found that the well-dispersed flexible ENP greatly enhanced the toughness of the epoxy with the cost of modulus and strength. Comparatively, the rigid silica nanoparticles improved Young's modulus, tensile strength and fracture toughness simultaneously. Both fumed and sol-gel-formed nanosilica particles conducted similar results in reinforcing the epoxy resin, although the latter exhibited almost perfect nanoparticle dispersion in matrix. The toughening mechanisms of nanocomposites were further discussed based on fractographic analysis.

Alignment of nanoparticles formed on the surface of 6H-SiC crystals irradiated by two collinear femtosecond laser beams

Nanoripples with periods of 150 and 80 nm are formed on the surface of 6H-SiC crystals irradiated by the p-polarized 800 nm and the s-polarized 400 nm femtosecond lasers, respectively. When both of the two collinear laser beams focus simultaneously on the sample surface, nanoparticles are formed on the whole ablation area, and they array in parallel lines. We propose and confirm that the second harmonics in the sample surface excited by the incident lasers plays an important role in the formation of nanostructures.

Effect of cerium oxide on the precipitation of silver nanoparticles in femtosecond laser irradiated silicate glass

We investigated the effect of cerium oxide on the precipitation of Ag nanoparticles in silicate glass via a femtosecond laser irradiation and successive annealing. Absorption spectra show that Ce3+ ions may absorb part of the laser energy via multiphoton absorption and release free electrons, resulting in an increase of the concentration of Ag atoms and a decrease of the concentration of hole-trapped color centers, which influence precipitation of the Ag nanoparticles. In addition, we found that the formed Ag-0 may reduce Ce4+ ions to Ce3+ ions during the annealing process, which inhibits the growth of the Ag nanoparticles.

Formation mechanisms of uniform arrays of periodic nanoparticles and nanoripples on 6H-SiC crystal surface induced by femtosecond laser ablation

Uniform arrays of periodic nanoparticles with 80-nm period are formed on 6H-SiC crystal irradiated by circularly polarized 400-nm femtosecond laser pulses. In order to understand the formation mechanism, the morphology evolvement as a function of laser pulse energy and number is studied. Periodic nanoripples are also formed on the sample surface irradiated by linearly polarized 400-, 510- and 800-nm femtosecond laser pulses. All these results support well the mechanism that second-harmonic generation plays an important role in the formation of periodic nanostructures.