Synthesis and characterization of ZnS:Mn2+ nano-particles for white-light emitting

The sol-gel method was used to obtain a kind of white-light emitting ZnS:Mn2+ nanoparticles capped by methacrylic acid with an average particle size of approximately 7 nm. The photoluminescence spectra, X-ray diffraction spectra, Fourier transform infrared reflection spectra and ultraviolet absorption spectra were used to measure their optical properties and crystal structures. The ZnS:Mn2+ nanoparticles with 0.58 wt% Mn2+ concentration emitted white light when excited by 380 nm. The PL spectrum exhibits two emission peaks under irradiation: one at 480 nm generated from the ZnS matrix, and one at 590 nm emitted by the doped Mn2+ ions. The nanoparticles will only emit white light with the optimum Mn2+ concentration (0.58 wt%). X-ray diffraction demonstrates the synthesized ZnS:Mn2+ nanoparticles have zinc blend crystal structure, and the infrared patterns of the capped ZnS:Mn2+ nanoparticles and methacrylic acid are comparable, indicating that the methacrylic polymer has capped or modified ZnS:Mn2+ nanoparticles.     

Synthesis and optoelectrochemical properties of ZnS:Mn nanocrystals

Mn2+ ions doped ZnS semiconductor nanocrystals (ZnS:Mn NCs) were synthesized using colloidal chemical method at 70 degrees C without any capping agents. The as-prepared undoped ZnS and ZnS:Mn NCs were characterized by UV-Vis absorption spectra, fluorescent emission spectra, X-ray powder diffraction (XRD), inductively coupled plasma analysis (ICP), X-ray photoelectron spectroscopy (XPS), Dynamic light scattering (DLS), cyclic voltammogram and electronic transmission microscopy (TEM). The dependence of photoluminescence of ZnS:Mn NCs on dopant concentration was studied. The results show that Mn2+ ions mainly stay at ZnS nanocystal surface, and Mn2+-surface defect state complex was formed, as a result of which, surface defect emission of ZnS nanocrystals was substituted with Mn2+-related PL emission. The strongest fluorescent emission intensity was obtain at 1.85 at% Mn2+ doped ZnS:Mn NCs. The Mn2+ doped ZnS:Mn NCs are of 5 nm in diameter. The emission peak at 575 nm is attributed to d-d (4T1 --> 6A1) transition of Mn2+ ions. The existence of Mn2+-related photoluminescence could be well correlated with cyclic voltammogram of Mn2+-doped NCs, where pair of oxidation and reduction peaks were clearly observed due to the doped Mn2+ ions. The adsorbed Mn2+ ions on ZnS NCs produced neither Mn2+ emission nor redox peaks. For heavily doped ZnS:Mn NCs (4.87 at%), redox peaks gap in cyclic voltammogram became larger and new oxidation peak appeared. Correspondingly, when the Mn2+ doping concentration reached 4.87 at%, the Mn2+-related emission totally disappears due to the Mn-Mn interactions. This work implys that electrochemical technique is possibly an useful tool to probe the local structure of doped Mn2+ ions.     

Photoluminescence decay kinetics of doped ZnS nanophosphors

Doped nanophosphor samples of ZnS:Mn, ZnS:Mn, Co and ZnS:Mn, Fe were prepared using a chemical precipitation method. Photoluminescence (PL) spectra were obtained and lifetime studies of the nanophosphors were carried out at room temperature. To the best of our knowledge, there are very few reports on the photoluminescence investigations of Co-doped or Fe-doped ZnS:Mn nanoparticles in the literature. Furthermore, there is no report on luminescence lifetime shortening of ZnS:Mn nanoparticles doped with Co or Fe impurity. Experimental results showed that there is considerable change in the photoluminescence spectra of ZnS:Mn nanoparticles doped with X (X = Co, Fe). The PL spectra of the ZnS:Mn, Co nanoparticle sample show three peaks at 410, 432 and 594?nm, while in the case of the ZnS:Mn, Fe nanoparticle sample the peaks are considerably different. The lifetimes are found to be in microsecond time domain for 594?nm emission, while nanosecond order lifetimes are obtained for 432 and 411?nm emission in ZnS:Mn, X nanophosphor samples. These lifetimes suggest a new additional decay channel of the carrier in the host material.     

Multicolor luminescence from transition metal ion (Mn2+ and Cu2+) doped ZnS nanoparticles

Mn and Cu doped ZnS nanoparticles in powder form were prepared by a simple solvothermal route. Particle size and crystal structure of the products were investigated through X-ray diffraction study revealing the formation of cubic ZnS nanoparticles of average diameter 2.5 nm. Particle size was also verified by the high resolution transmission electron microscopic images. Blue emission at approximately 445 nm was observed from the undoped sample, which was attributed to the presence of large surface defects. With increasing doping concentration the defect related emission gradually quenches and subsequently the impurity related emissions appeared. Mn doped samples exhibited orange emission at approximately 580 nm which may be attributed to the transition between (4)T1 and (6)A1 energy levels of the Mn2+ 3d states. Whereas, the Cu doped ZnS nanoparticles exhibited a red shifted strong blue emission at approximately 466 nm which is attributed to the transition of the electrons from the surface states to the 't2' levels of Cu impurities.     

Temperature dependence of up-conversion luminescence and photoluminescence of Mn2+ in ZnS:Mn2+ nanoparticles

The photoluminescence (excited at both 300 nm and 383.5 nm) and up-conversion luminescence (excited at 767 nm) of the Mn2+ 4T1-->6A1 transition in both bulk and ZnS:Mn2+ nanoparticles have been measured as a function of temperature. The Mn2+ emission spectra shift monotonically to longer wavelengths at lower temperatures, whereas the intensity change of the luminescence is more complex. The complicated temperature behavior is explained by considering the processes of nonradiation relaxation via phonon coupling, exciton thermal dissociation (binding energy), energy transfer, carrier trapping, and the temperature change of the absorption spectra. The fact that the temperature dependence of the 767 nm excited up-conversion luminescence is the same as the 383.5 nm excited photoluminescence in both bulk and nanoparticles supports the conclusion that the up-conversion luminescence is due to two-photon absorption.     

Luminescent properties of ZnS:Mn2+/ZnS core/shell nanocrystals

High-quality ZnS:Mn2+/ZnS core/shell nanocrystals (NCs) with a core crystal diameter of 6.1 nm and 1.15 nm thick shells were synthesized via a high-boiling solvent process. The energy levels of the conduction band and valance band are estimated to be -3.2 eV and -6.8 eV by cyclic voltammetry and ultraviolet-visible (UV-vis) absorption spectra. The ZnS:Mn2+/ZnS NC emission peak is primarily located at 580 nm under 310 nm light excitation, originating from the charge transition from 4T1 to 6A1 within the 3d5 configuration of the Mn2+ ion. Based on ZnS:Mn2+/ZnS NCs as the active layer electroluminescent devices, the emission peak mainly locates at 460 nm with one shoulder emission peaking at 580 nm. The photoluminescence and electroluminescence properties of ZnS:Mn2+/ZnS NCs are investigated in the view of charge carrier injection and energy level alignment.     

Time resolved spectroscopic studies on some nanophosphors

Time resolved spectroscopy is an important tool for studying photophysical processes in phosphors. Present work investigates the steady state and time resolved photoluminescence (PL) spectroscopic characteristics of ZnS, ZnO and (Zn, Mg)O nanophosphors both in powder as well as thin film form. Photoluminescence (PL) of ZnS nanophosphors typically exhibit a purple/blue emission peak termed as self activated (SA) luminescence and emission at different wavelengths arising due to dopant impurities e.g. green emission for ZnS: Cu, orange emission for ZnS: Mn and red emission for ZnS: Eu. The lifetimes obtained from decay curves range from ns to ms level and suggest the radiative recombination path involving donor-acceptor pair recombination or internal electronic transitions of the impurity atom. A series of ZnMgO nanophosphor thin films with varied Zn: Mg ratios were prepared by chemical bath deposition. Photoluminescence (PL) excitation and emission spectra exhibit variations with changing Mg ratio. Luminescence lifetime as short as 10⁻¹⁰ s was observed for ZnO and ZnMgO (100: 10) nanophosphors. With increasing Mg ratio, PL decay shifts into microsecond range. ZnO and ZnMgO alloys up to 50% Mg were prepared as powder by solid state mixing and sintering at high temperature in reducing atmosphere. Time resolved decay of PL indicated lifetime in the microsecond time scale. The novelty of the work lies in clear experimental evidence of dopants (Cu, Mn, Eu and Mg) in the decay process and luminescence life times in II–VI semiconductor nanocrystals of ZnS and ZnO. For ZnS, blue self activated luminescence decays faster than Cu and Mn related emission. For undoped ZnO nanocrystals, PL decay is in the nanosecond range whereas with Mg doping the decay becomes much slower in the microsecond range.     

Paramagnetic nature of Mn doped ZnS nano particles in opto electronic device application

Manganese (Mn²⁺) doped ZnS nano sized powder was prepared by co precipitation method with different concentration from 1 to 5 %. The X-ray diffraction pattern indicates that the prepared powders are in cubic structure with the crystallite sizes lie in the range of 10–12 nm. Diffuse reflectance studies enlightens that an increment in the band gap (3.38–3.55 eV) with increasing dopant. The morphology and size of the sample could be intuitively determined by field emission scanning electron microscope and it shows that ZnS and Mn doped ZnS nanoparticles are appeared as spherical shape. The replacement of Zn by Mn is confirmed by energy dispersive analysis. TEM images confirm the spherical shape of the nanoparticles and SAED images exhibit the crystalline nature and confirm the cubic nature of the synthesized samples. The prepared luminescent nanoparticles of Mn doped ZnS have emission peak at around 617 nm. The symmetry and electronic structure of the Mn doped samples are studied with electron paramagnetic resonance.The paramagnetic nature of Mn doped ZnS nano particles are validated by using vibrating sample magnetometer spectra at room temperature. Thermal analysis measurement of the samples shows that the thermal stability of Mn doped ZnS is higher than the undoped ZnS. This corroborates that ZnS:Mn doping is attributed to the removal of water and it enhanced the crystallinity.     

Photoluminescence decay dynamics and mechanism of energy transfer in undoped and Mn2+ doped ZnSe nanoparticles

Energy transfer dynamics in Mn2+-doped ZnSe nanoparticles have been studied by monitoring the photoluminescence using time-integrated and time-resolved spectroscopic techniques. Upon Mn2+ doping, static photoluminescence (PL) spectra show that the bandedge excitonic state is quenched and the characteristic Mn2+ emission appears at 584 nm. Picosecond PL kinetics and femtosecond transient absorption studies have both found that the Mn2+ doping substantially shortens the average lifetimes of the bandedge excitonic state as well as shallow trap states. The energy transfer from ZnSe to Mn2+ likely follows two mechanisms, one mediated through trap states and another without.     

Optical properties of Mn-doped ZnS semiconductor nanoclusters synthesized by a hydrothermal process

Undoped and Mn-doped ZnS nanoclusters have been synthesized by a hydrothermal approach. Various samples of the ZnS:Mn with 0.5, 1, 3, 10 and 20 at.% Mn dopant have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-ray, high resolution electron microscopy, UV-vis diffusion reflection, photoluminescence (PL) and photoluminescence excitation (PLE) measurements. All the prepared ZnS nanoclusters possess cubic sphalerite crystal structure with lattice constant a = 5.408 ± 0.011 ?. The PL spectra of Mn-doped ZnS nanoclusters at room temperature exhibit both the 495 nm blue defect-related emission and the 587 nm orange Mn²⁺ emission. Furthermore, the blue emission is dominant at low temperatures; meanwhile the orange emission is dominant at room temperature. The Mn²⁺ ion-related PL can be excited both at energies near the band-edge of ZnS host (the UV region) and at energies corresponding to the Mn²⁺ ion own excited states (the visible region). An energy schema for the Mn-doped ZnS nanoclusters is proposed to interpret the photoluminescence behaviour.     

Structural and optical properties of Co-doped ZnS nanoparticles synthesized by a capping agent

Cobalt-doped Zinc sulfide (ZnS) nanoparticles were prepared by a simple chemical method using alkyl hydroxyl ethyl dimethyl ammonium chloride (YH) as capping agent. The structural and optical properties of prepared cobalt-doped ZnS nanoparticles have been characterized. X-ray diffraction patterns and transmission electron microscope images reveal pure cubic ZnS phase with size of about 5–2 nm for all cobalt-doped ZnS nanoparticles. The lattice constant of the samples decreases slightly by the introduction of Co²⁺ The absorption edge of the ZnS:Co²⁺ nanoparticles is blue-shifted as compared with that of bulk ZnS, indicating the quantum confinement effect. The photoluminescence emission band exhibits a blue shift for Co-doped ZnS nanoparticles as compared to the ZnS nanoparticles.     

Photoluminescence and field emission properties of ZnS:Mn nanoparticles synthesized by rf-magnetron sputtering technique

Nanoparticles of ZnS:Mn have been grown by radio frequency magnetron sputtering technique on glass and Si substrates at a substrate temperature 300 K. X-ray diffraction patterns and selected area electron diffraction patterns confirmed the nanocrystalline cubic ZnS phase formation. TEM micrographs of the films revealed the manifestation of ZnS:Mn nanoparticles with an average size 6 nm. UV–Vis–NIR spectrophotometric measurement showed that the films are highly transparent (90%) in the wavelength range 400–2600 nm. From the measurements of transmittance spectra of the films the direct allowed bandgap values have been calculated and they lie in the range 3.89–4.12 eV. The bandgap decreased with the increase of Mn concentration in the films. The Mn concentrations in the films have been varied from 0% to 8.9% and was measured by energy dispersive X-ray analysis. The photoluminescence of the Mn doped ZnS nanoparticles was measured. The intensity of the PL peaks at first increased with the increase of Mn concentration in the films up to 3.8% of Mn doping and at a Mn concentration higher than this, the intensity of PL peak decreased. Nanocrystalline ZnS:Mn showed good field emission property with a turn on field lying in the range 5.26–6.78 V/μm for a variation of anode to sample distance from 60 μm to 100 μm.     

Wurtzite-type ZnS nanoparticles by pulsed electric discharge

The synthesis of wurtzite-type ZnS nanoparticles by an electric discharge submerged in molten sulfur is reported. Using a pulsed plasma between two zinc electrodes of diameter 5 mm in molten sulfur, we have synthesized high-temperature phase (wurtzite-type) ZnS nanocrystals with an average size of about 20 nm. The refined lattice parameters of the synthesized wurtzite-type ZnS nanoparticles were found to be larger than those of the reported ZnS (JCPDS card no 36-1450). Synthesis of ZnMgS (solid solution of ZnS and MgS) was achieved by using ZnMg alloys as both cathode and anode electrodes. UV-visible absorption spectroscopy analysis showed that the absorption peak of the as-prepared ZnS sample (319 nm) displays a blue-shift compared to the bulk ZnS (335 nm). Photoluminescence spectra of the samples revealed peaks at 340, 397, 423, 455 and 471 nm, which were related to excitonic emission and stoichiometric defects.     

Effect of annealing on the structural and optical properties of non-coated and silica-coated ZnS:Mn nanoparticles

The Mn²⁺-doped ZnS nanoparticles stabilized by sodium citrate were synthesized through a simple chemical route. Using the ZnS:Mn nanoparticles as seeds, the silica-coated ZnS:Mn nanocomposites were formed in isopropanol by the controlled hydrolysis of tetraethyl orthosilicate. The photoluminescence spectra confirmed that the Mn²⁺ ions were incorporated into the ZnS nanoparticles. The annealing effect on the structural and optical properties of these particles was studied over a range of 100–400 °C. The results of X-ray diffraction and photoluminescence showed that the silica shell not only improved the thermal stability but also resisted the lattice-deformation and oxidation of the particles. The thermal analysis further confirmed that the non-coated ZnS:Mn nanoparticles were unstable beyond 200 °C.     

Photoluminescent properties of ZnS:Mn nanoparticles with in-built surfactant

Mn-doped ZnS nanoparticles, having average diameter 3–5 nm, have been synthesized using chemical precipitation technique without using any external capping agent. Zinc blende crystal structure has been confirmed using the X-ray diffraction studies. The effect of various concentrations of Mn doping on the photoluminescent properties of ZnS nanoparticles has been studied. The time-resolved photoluminescence spectra of the ZnS:Mn quantum dots have been recorded and various parameters like lifetimes, trap depths, and decay constant have been calculated from the decay curves at room temperature. The band gap was calculated using UV–Visible absorption spectra.     

Luminescence properties of nano-sized Sr2MgSiO5: Eu2+, Mn2+ phosphors prepared by the sol-gel method

Nano-sized Sr2MgSiO5:Eu2+, Mn2+ phosphor was synthesized by the sol-gel method. The preparation conditions of the precursor were determined. The effect of Eu2+ and Mn2+ content on the luminescence intensity was studied. X-ray diffraction (XRD), photoluminescence spectra (PL), and photoluminescence excitation spectra (PLE) were used to characterize the samples. The results showed that the excitation bands ranged from 250 to 450 nm, and their peaks positioned around 365 nm. The emission spectrum consists of three bands: blue, green, and red, respectively. The blue and green emission bands originate from the center of the Eu2+, while the red emission band is attributed to the energy transfer from Eu2+ to Mn2+. White light can be obtained by mixing the three emission colors. The experiment results show that the Sr2MgSiO5:Eu2+, Mn2+ is a single host phosphor with superior properties for use in white light emitting diodes (white LED).     

Effect of annealing on the morphology and properties of ZnS:Mn nanoparticles/PVP nanofibers

As one kind of new optoelectronic materials, ZnS:Mn nanoparticles/PVP composite nanofibers are prepared by the electrospinning technique successfully. SEM, XRD, FT-IR spectroscopy, photoluminescence and TEM measurements are employed in the study. By the method of annealing, the effect on the morphology and properties of the composite nanofibers is studied. After annealing treatment, the separating state of the nanofibers is improved obviously, ZnS:Mn nanoparticles are well dispersed in the nanofiber, the PL peak originated from ⁴T₁→⁶A₁ transition of Mn ions shifts from 605 nm to 599 nm. The existence of orange emission peaks confirms that ZnS:Mn nanoparticles are formed in the fibers.     

Ion beam synthesis of compound nanoparticles in SiO2

The ion beam synthesis of group IV (SiC) and II–VI (ZnS) compound nanoparticles in SiO₂ layers is studied. These systems are potentially interesting for optoelectronic applications such as electroluminescent devices emitting in the visible and UV range. The combination of structural (transmission electron microscopy, electron and X-ray diffraction), optical (infrared and raman spectroscopies, optical absorption and photoluminescence) and physico-chemical (X-ray photoelectron spectroscopy, secondary ion mass spectroscopy) techniques have been used to identify the phases formed and to correlate the optical behaviour of the layers with their microstructure. The first part is dedicated to the synthesis of luminescent SiO₂ layers co-implanted with Si and C. The presence of regions with different composition in terms of C content gives rise to the formation of 3 types of nanoparticles (Si, C and SiC) leading to three intense, simultaneous and independent emission bands covering the whole visible range. A second part is dedicated to the synthesis of Mn doped ZnS nanocrystals. We have succeeded in synthesizing ZnS nanocrystals by sequential ion implantation in SiO₂. The structural characterization of the annealed layers shows ZnS precipitates having a wurtzite-2H structure and with a quite narrow distribution of sizes. This population of nanocrystals is organized in two layers parallel to the free surface, as a consequence of a pure Ostwald ripening process or as a result of the implantation damage distribution. The optical analysis of samples co-implanted with Mn shows the presence of a yellow-green and intense photoluminescence corresponding to an intra- Mn²⁺ transition, which demonstrates the effective doping with Mn of the ZnS precipitates.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles

ZnS quantum dots of size 3 nm are prepared at 303 K using ZnSO₄ and Na₂S₂O₃ precursors with thioglycerol as stabilizing agent. Cd²⁺ doped ZnS were prepared by varying doping concentration from 1 to 8 wt.%. ZnS quantum dots were mixed with CdS quantum dots of size 4 nm in the 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 M ratio. The nanoparticles were characterized by UV–vis, photoluminescence (PL), XRD and high-resolution TEM measurements. The XRD pattern, high-resolution TEM image and SAED pattern reveal that the nanoparticles are in well-crystallized cubic phase. The band gap of ZnS has increased from the bulk value 3.7 to 4.11 eV showing quantum size effect. Excitonic transition is observed at 274 nm in UV absorption and PL emission at 411 nm. Doping with Cd²⁺ red-shifts both UV and PL spectral bands and enhances the PL band of ZnS nanoparticles. Mixing CdS and ZnS quantum dots in different molar ratios shows red-shift of the band edge in the CdS/ZnS hybrid system. In the 1:1 hybrid system of CdS/ZnS nanoparticles, PL band is red-shifted and the intensity is almost doubled with respect to that of CdS nanoparticles.     

Strong green luminescence of Mg-doped ZnO nanowires

The ZnO nanowires doped with Mg (Mg-ZnONWs) were produced by thermally oxidizing Zn and Mg powders. TEM and XRD patterns indicated that Mg-ZnONWs were crystalline with a wurzite structure. The Mg doping was confirmed with XPS measurements. The green emission band at 500 nm in the photoluminescence spectrum of Mg-ZnONWs and peaks at 366 nm in low intensity were observable. Raman spectrum indicated that oxygen deficiency was not the dominant factor for the green emission. The green emission was further directly observed with a digital camera.