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.     

Effect of heat-treatment on CdS and CdS/ZnS nanoparticles

Mono-dispersed and spherical cadmium sulfide (CdS) nanoparticles and cadmium sulfide/zinc sulfide (CdS/ZnS) nanoparticles, 4–5 nm in diameter, were synthesized in a heptane-AOT-water microemulsion system. The heat treatment of CdS and CdS/ZnS nanoparticles was annealed at 570 °C under the air atmosphere. The heat-treated nanoparticles were of variable large sizes and had enhanced crystallinity. UV–Vis spectra of heat-treated CdS and CdS/ZnS nanoparticles revealed a flat shape similar to that of bulk CdS compounds. The difference between the PL emission bands of organic-coated nanoparticles and heat-treated nanoparticles was small. The PL emission energy of heat-treated nanoparticles was improved by about 2–3 times compared with that of organic-coated nanoparticles.     

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.     

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.     

Effect of zinc oxide concentration in fluorescent ZnS:Mn/ZnO core–shell nanostructures

In the present work, we have prepared zinc sulphide (ZnS:Mn)/zinc oxide (ZnO) core–shell nanostructures by a chemical precipitation method and observed the effect of ZnO concentration on the fluorescent nanoparticles. Change in the morphological and optical properties of core–shell nanoparticles have been observed by changing the concentration of ZnO in a core–shell combination with optimum value of Mn to be 1 % in ZnS. The morphological studies have been carried out using X-ray diffraction (XRD) and transmission electron microscopy. It was found that diameter of ZnS:Mn nanoparticles was around 4–7 nm, each containing primary crystallites of size 2.4 nm which was estimated from the XRD patterns. The particle size increases with the increase in ZnO concentration leading to the well-known ZnO wurtzite phase which was coated on the FCC phase of ZnS:Mn. Band gap studies were performed by UV–visible spectroscopy and a red shift in absorption spectra have been observed with the addition of Mn as well as with the capping of ZnO on ZnS:Mn. The formation of core–shell nanostructures have been also confirmed by FTIR analysis. Photoluminescence studies show that emission wavelength is red shifted with the addition of ZnO layer on ZnS:Mn(1 %). These core–shell ZnS:Mn/ZnO nano-composites will be a very suitable material for specific kind of tunable optoelectronic devices.     

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.     

Electrical conductivity of doped ZnS

The electrical conductivity of doped ZnS with different impurities (Mn, Fe, Co, Ni and Cu) of various concentrations has been measured to verify the existence of ladder-like levels of ‘killers’ of luminescence. Attempts have been made to ascertain the separation between the valence band of the host ZnS and the ground state of the acceptor impurities and also to investigate the effect of various concentrations of impurities on the electrical conductivity of doped ZnS.     

Synthesis and characterization of sol-gel derived ZnS : Mn2+ nanocrystallites embedded in a silica matrix

Synthesis and characterization of undoped and Mn²⁺ doped ZnS nanocrystallites (radius 2–3 nm) embedded in a partially densified silica gel matrix are presented. Optical transmittance, photoluminescence (PL), ellipsometric and electron spin resonance measurements revealed manifestation of quantum size effect. PL spectra recorded at room temperature revealed broad blue emission signal centred at ∼ 420 nm and Mn²⁺ related yellow-orange band centred at ∼ 590 nm while ESR indicated that Mn in ZnS was present as dispersed impurity rather than Mn cluster.     

Triboluminescent properties of zinc sulfide phosphors due to hypervelocity impact

The emission of light due to crystal fracture, or triboluminescence (TL), is a phenomenon that has been known for centuries. One of the most common examples of TL is the flash created from chewing Wint-O-Green Lifesavers^®. From 2004 to 2006, research was completed using the two-stage light gas gun located at the NASA Marshall Space Flight Center (MSFC) in Huntsville, Alabama to measure the TL properties for zinc sulfide doped with both manganese (ZnS:Mn) and copper (ZnS:Cu). Results clearly show that hypervelocity impact-induced TL has been observed for both ZnS:Mn and ZnS:Cu. For ZnS:Mn, TL produced during 4.7 and 5.7 km/s impacts was statistically more luminous than was observed from similar data collected at 3.3 km/s. The TL decay time for ZnS:Mn was found to be 292 ± 58 μs, which is totally consistent with earlier measurements that did not use impact as an excitation source. Further, the emission of TL from ZnS:Mn undergoing hypervelocity impact has been demonstrated to have a significant component at the known peak emission wavelength of ZnS:Mn of 585 nm. Small TL emission generated as a result of hypervelocity impact was also observed from ZnS:Cu. The most intriguing conclusion from this research is that it may be possible to discriminate impact velocity by measuring the time-integrated luminosity of TL phosphors. An ability to measure the velocity of a hypervelocity impact is a significant indicator of the potential usefulness for this concept for use as an impact sensor in future spacecraft.     

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.     

Structural and electrical conductivity studies on nanocrystalline undoped and silver doped zinc sulphide

Zinc sulphide (ZnS) and silver doped zinc sulphide nanocrystallites (ZnS:Ag) of average size 4 and 8 nm, respectively, have been synthesized by chemical precipitation technique. The structural and morphological studies using X-ray and high resolution transmission electron microscopy (HRTEM) measurements have confirmed hexagonal structure for the samples. Using the impedance spectroscopy method, the effect of grain interior and electrode–sample interface effect on their conductivity have been studied at various temperatures. In high temperature region, the electrode–sample interface effect is found to be larger than that of the grain interior region. Further, the results of the activation energies of the charge carriers in both the regions are determined and analyzed. The conduction mechanism of silver doped zinc sulphide nanocrystallites has been studied at various temperatures and the results are reported.     

Optical properties of CdS sintered film

Chemical method has been used to prepare cadmium sulphide by using cadmium, hydrochloric acid and H₂S. The reflection spectra of covered and uncovered sintered films of CdS have been recorded by ‘Hitachi spectrophotometer’ over the wavelength range 300–700 nm. The energy band gaps of these films have been calculated from reflection spectra. It is found that the energy band gap of both films is same as 2.41 eV. It is indicated that energy band gap of these films does not change. This value of band gap is in good agreement with the value reported by other workers. The measurement of photocurrent has also been carried out using Keithley High Resistance meter/ Electrometer. This film shows the high photosensitivity and high photocurrent decay. Thus so obtained films are suitable for fabrication of photo detectors and solar cells.     

Charge transfer model for generation of ZnS: Mn nanocrystalline luminophore emission

Time dependencies of photoluminescence decay of the powder luminophore consisting of ZnS nanoparticles doped with Mn in micro- and millisecond range were registered experimentally. It was shown that the experimental decay curves could not be correctly described in the framework of the existing models. A simple model was suggested describing the kinetics of photoluminescence decay kinetics with participation of Mn centers that included the possibility of electron transfer between ZnS nanoparticles.     

Characterization of mono- and multilayered films with Mn-doped ZnS nanoparticles and luminescence properties of the monolayered films prepared by applying magnetic fields

Mn²⁺-doped ZnS (ZnS:Mn) nanoparticles were prepared using bis(2-ethylhexyl) sulfosuccinate (AOT) reversed micelle method. Luminescence at 583-589 nm were observed in the ZnS:Mn nanoparticles and are ascribed to Mn²⁺ ion in the nanoparticles due to energy transfer from ZnS. The luminescence was enhanced by capping with alkanethiol. Mono-and multilayered films with the alkanethiol-capped ZnS:Mn nanoparticles were fabricated on quartz substrates by layer-by-layer method using self-assembled monolayer (SAM) of 1,6-hexanedithiol. The polarization degrees of luminescence for the monolayered films were enhanced by preparation under applying magnetic field. The enhancements are probably caused by magnetic orientation of the ZnS:Mn nanoparticles on the quartz substrates.     

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.     

Luminescence in Mn-doped CdS nanocrystals

We have synthesized Mn-doped CdS nanocrystals (NCs) with size ranging from 1.8–3 nm. Photoluminescence (PL) spectra of the doped NCs differ from that of the undoped NCs with an additional peak due to Mn d-d transitions. Electron paramagnetic resonance spectra along with X-ray absorption spectroscopy and PL spectra confirm the incorporation of Mn in the CdS lattice. The fact that emissions from surface states and the Mn d levels occur at two different energies, allowed us to study the PL lifetime decay behaviour of both kinds of emissions.     

The light emission properties of ZnS:Mn nanoparticles

ZnS and Mn-doped ZnS nanoparticles were synthesized via a simple hydrothermal synthesis method. The former emits super bright blue fluorescence light while the latter exhibits super-bright yellow light under a fluorescence microscope. Accordingly, their photoluminescence peaks are located at 420 nm and 580 nm in the spectra excited with 281 nm and 335 nm wavelengths, respectively. The super-bright ZnS:Mn nanoparticles can be used as a yellow fluorescence powder in making LED and plat display, and can be used as biological fluorescence probe to replace CdSe, CdS quantum dos without any damage to mankind and environment.     

Tuning photoluminescence of ZnS nanoparticles by silver

We report the results of investigation of the interaction of silver with presynthesized ZnS nanoparticles (NPs) that was stabilized by cetyl trimethyl ammonium bromide (CTAB). The photoluminescence properties of ZnS NPs were followed in the presence of Ag⁺ ions, Ag NPs and by the synthesis of Ag@ZnS core-shell nanoparticles. We observed that CTAB stabilized ZnS NPs emitted broadly in the region from 350–450 nm, when excited by 309 nm light. In the presence of Ag⁺ ions the emission peak intensity up to 400 nm was reduced, while two new and stronger peaks at 430 nm and 550 nm appeared. Similar results were obtained when Ag NPs solution was added to ZnS solution. However, when Ag@ZnS NPs were synthesized, the emission in the 350–450 nm region was much weaker in comparison to that at 540 nm, which itself appeared at a wavelength shorter than that of Ag⁺ ion added ZnS NPs. The observations have been explained by the presence of interstitial sulfur and Zn²⁺, especially near the surface of the nanocrystals and their interaction with various forms of silver. In addition, our observations suggest that Ag⁺ ions diffuse into the lattice of the preformed ZnS NPs just like the formation of Ag⁺ doped ZnS NPs and thus changes the emission characteristics. We also have pursued similar experiments with addition of Mn²⁺ ions to ZnS and observed similar results of emission characteristics of Mn²⁺ doped ZnS NPs. We expect that results would stimulate further research interests in the development of fluoremetric metal ion sensors based on interaction with quantum dots.     

Preparation of CdS and ZnS nanoparticles using microwave irradiation

Nanoparticles of CdS, ZnS have been prepared by a very simple fast reaction between CdCl₂ or Zn(Ac)₂ and thioacetamide in aqueous solution using microwave irradiation. The nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), reflectance and photoluminescence spectra. The sizes of the sample as prepared were calculated by Debye–Scherrer formula according to XRD spectra to be about 9 and 3 nm for CdS and ZnS, respectively. Similar results can also been obtained in the TEM images.     

Preparation and characterization of titania/ZnS core-shell nanotubes

Core-shell nanocomposites of titania nanotubes/ZnS quantum dots have been prepared by using a hydrothermal synthetic method and characterized by using various microscopic and spectroscopic methods. ZnS quantum dots surround the outsides of titania nanotubes having the inner and the outer diameters of 15 and 30 nm, respectively, with a thickness of 2 nm. The nanocomposites suspended in water show a broader absorption spectrum shifted to a longer wavelength by 20 nm and emit substantially stronger ZnS luminescence having significantly slower decay kinetics than bare ZnS nanoparticles in water. The support of TiO2 nanotubes is found to enhance the optical properties of ZnS considerably.