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.     

Effect of inorganic shells on luminescence properties of ZnS:Ag nanoparticles

The hydrothermally synthesized Ag-doped ZnS (ZnS:Ag) nanoparticles have been coated with inorganic shells by a chemical precipitation method. The ZnS:Ag/ZnS, ZnS:Ag/CdS, and ZnS:Ag/ZnO core–shell nanoparticles with different thickness of ZnS, CdS, and ZnO shells have been prepared. The effects of shells on the luminescence properties of ZnS:Ag cores have been investigated through the photoluminescence (PL) spectra and luminescence stabilities of products. In the core–shell nanoparticles involved here, the ZnO shell can most significantly enhance the luminescence of ZnS:Ag cores. The 450 nm emission intensity of ZnS:Ag/ZnO nanoparticles is up to 125 % of that of ZnS:Ag nanoparticles. However, the ZnO shell can hardly influence the luminescence stability under ultraviolet irradiation. The ZnS shell can only increase the luminescence of ZnS:Ag cores to some extent, but it can improve the luminescence stability under ultraviolet irradiation. Although the CdS shell can improve the luminescence stability to some extent, it quenches the luminescence of ZnS:Ag nanoparticles dramatically.     

Effect of activator distribution on photo- and X-ray excited luminescence properties of ZnS:Cu,Cl phosphors

ZnS:Cu,Cl phosphors were prepared by conventional solid state reaction with the aid of NaCl-MgCl₂ flux. The copper activator was introduced into the phosphor precursors by three different methods: co-precipitated with ZnS (CP), wet-coated onto ZnS powders (WC), and simply mixed with ZnS in a mortar (SM). The samples were characterized by X-ray powder diffraction, photoluminescence spectra and X-ray excited luminescence spectra. The results show that both photo- and X-ray excited luminescence intensities of the as-prepared ZnS:Cu,Cl phosphors are in the decreasing order of CP > WC > SM. The different copper activator distribution in the phosphors resulting from the different methods was the main reason responsible for the different luminescence intensity, and uniform distribution is beneficial to the luminescence of the phosphors.     

Highly porous ZnS microspheres for superior photoactivity after Au and Pt deposition and thermal treatment

This work highlights the enhanced photocatalytic activity of porous ZnS microspheres after Au and Pt deposition and heat treatment at 500 °C for 2 h. Microporous ZnS particles of size 2–5 μm with large surface area 173.14 m² g⁻¹ and pore volume 0.0212 cm³ g⁻¹ were prepared by refluxing under an alkaline medium. Photoluminescence of ZnS at 437 nm attributed to sulfur or zinc vacancies were quenched to 30% and 49%, respectively, after 1 wt% Au and Pt loading. SEM images revealed that each ZnS microparticle consist of several smaller ZnS spheres of size 2.13 nm as calculated by Scherrer's equation. The rate of photooxidation of 4-nitrophenol (10 μM) under UV (125 W Hg arc–10.4 mW/cm²) irradiation has been significantly improved by Au and Pt deposition followed by sintering due to better electron capturing capacity of deposited metals and growth of crystalline ZnS phase with less surface defects.     

Synthesis and characterization of water-soluble <Emphasis Type="SmallCaps">l</Emphasis>-cysteine-modified ZnS nanocrystals doped with silver

The water-soluble Ag⁺-doped ZnS nanocrystals surface capped with cysteine (expressed as ZnS:Ag/Cys) were synthesized in aqueous solution by using l-cysteine as surface modifier. The crystal structure, size, shape, component, and spectral properties of ZnS:Ag/Cys nanocrystals were characterized by X-ray power diffraction, transmission electron microscope, energy dispersive X-ray analysis, inductively coupled plasma atomic emission spectrometry, infrared spectrum, UV–Vis absorption spectrum, and photoluminescence spectrum. The results show that the spherical ZnS:Ag/Cys nanocrystals with an average diameter of 2.6 nm have good fluorescent characteristics, their fluorescence intensity is enhanced greatly after doped with Ag⁺. And the sulfur atoms in cysteine molecules are coordinated with metal ions on the surface of the nanocrystals, the cysteine modified on the surface of ZnS:Ag/Cys nanocrystals renders the nanocrystals water soluble and biocompatible. The ZnS:Ag/Cys nanocrystals have potential applications in molecular assembly and biological fluorescence analysis.     

Optical properties of water-soluble Co:ZnS semiconductor nanocrystals synthesized by a hydrothermal process

Water-soluble ZnS:Co²⁺ nanocrystals (NCs) were synthesized by a low temperature hydrothermal process using 3-mercaptopropionic acid (MPA) as capping agent and the influence of doping on the optical properties of ZnS:Co²⁺ NCs was investigated. It was found that the ZnS:Co²⁺ NCs are highly crystalline and show zinc blende structure with an average particle size of about 7 nm. The lattice constant of the ZnS:Co²⁺ NCs decreases slightly by the introduction of Co²⁺. The Co dopants were well doped into the ZnS:Co²⁺ NCs, as confirmed by X-ray photoelectron spectroscopy(XPS) and the ⁴A₂(F) → ⁴T₁(P) transition of Co²⁺ was detected from the UV-vis absorption spectra. The absorption edge of the ZnS:Co²⁺ NCs is blue-shifted as compared with that of bulk ZnS, indicating the quantum confinement effect. The PL intensity of the NCs shows the maximum value when the Fe-doping concentration is 0.5 at.%.     

Synthesis and photoluminescence properties of Cl-doped ZnS nanoparticles prepared by a solid-state reaction

ZnS:Cl⁻ nanoparticles with strong blue emission have been synthesized successfully by a solid-state reaction at low temperature. The dependence of photoluminescence (PL) properties of ZnS:Cl⁻ nanoparticles on the Cl⁻ contents was researched, and the influences of the annealing ambience and using polyvinyl alcohol (PVA) during the synthesis on the PL of ZnS:Cl⁻ (Cl/Zn = 0.35) nanoparticles were discussed. X-ray power diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and ultraviolet-visible spectroscopy were used to characterize their structure, chemical state, diameter, surface states, and PL properties. The results showed that ZnS:Cl⁻ nanoparticles had a cubic blende crystal structure and an average crystallite size of 17.40–19.16 nm. The most intensity blue emission peaking at about 425 nm was obtained when Cl/Zn = 0.35 under 330 nm excitation at room temperature. The emission intensity of ZnS:Cl⁻ (Cl/Zn = 0.35) was increased 3-fold than that of ZnS. The results showed that the PL of ZnS:Cl⁻ (Cl/Zn = 0.35) nanoparticles was enhanced after annealing or using PVA during the synthesis, and annealing in vacuum had a stronger effect in improving the luminescence properties of ZnS nanoparticles than in air. This work suggests that it is an effective method to improve the PL intensity of ZnS nanocrystals by doping with Cl⁻ in ZnS.     

Exceptionally large third-order optical susceptibility in Ag:SrBi2Nb2O9 composite films

Thin films of SrBi₂Nb₂O₉ with and without the inclusion of Ag nanocrystals were prepared on MgO (001) substrates by alternative pulsed laser ablation of SrBi₂Nb₂O₉ ceramic and Ag metal in a nitrogen atmosphere. The size of the Ag nanocrystals can be brought down to ca. 5.0 nm, as revealed by transmission electron microscopy and X-ray diffraction. We measured the third-order susceptibility χ⁽³⁾ of the deposits by single beam z-scan technique at a wavelength of 532 nm. It is found that SrBi₂Nb₂O₉ is an effectively nonlinear optical medium, exhibiting a very large χ⁽³⁾. With the inclusion of Ag nanocrystals the χ⁽³⁾ was nearly doubled (Reχ⁽³⁾ = 8.052 × 10^− 7 esu, and Imχ⁽³⁾ = − 1.717 × 10^− 7 esu), which comes very close to the maximum value available in the current time. This indicates that the Ag:SrBi₂Nb₂O₉ composite structure can be an excellent candidate for nonlinear optical applications. A general approach for further enhanced third-order susceptibility by tailoring the dielectric constant of the metal inclusion is briefly discussed.     

High-energy emission band nature in ZnS-type phosphors activated with silver and chlorine

The cathodoluminescence emission spectra of cubic blue-emitting ZnS:Ag, Cl, hexagonal green-emitting (Zn_0.675, Cd_0.325) S:Ag, Cl as well as hexagonal red-emitting (Zn_0.27, Cd_0.73) S:Ag, Cl phosphors have been measured at 293, 77 and 4.2 K. The measured spectra of the phosphors exhibited a single broad emission band at 293 K, while they had two emission bands at 77 and 4.2 K. The two emission bands shifted to a lower energy with increase of their corresponding half-widths as the temperature at which the spectra were measured was raised. The time-resolved emission spectra measured showed that the low-energy band also shifted in the lower energy direction during the decay of luminescence, confirming its donor-acceptor (DA) transition nature. The high-energy band decayed faster than the low-energy one and no energy shift occurred during its decay; it was attributed to donor-isoelectronic pair (DI) transition. The lifetimes of 0.625 and 4.2 µsec were estimated for high- and low-energy bands, respectively, in the emission spectra of ZnS:Ag, Cl at 4.2 K.     

Preparation and properties of thin ZnS:Cu films phosphors

Thin films of ZnS and ZnS:Cu were prepared by an original metalorganic chemical vapour deposition (MOCVD) method under atmospheric pressure onto a glass substrate heated up to 230–250 °C. The film thickness varied from 0.6 to 1 μm. The thin films were doped with Cu and Cl by the thermal treatment during 1 h at 600 °C at atmospheric pressure in the blend composed of a ZnS powder with Cu and Cl compounds. These films were used for fabrication of the thin film electroluminescent (TFEL) devices with a conventional double insulating structure. The structural properties were investigated by use of X-ray diffraction (XRD) techniques and atomic force microscopy (AFM). Electroluminescent (EL) spectra, electrical and EL characteristics were investigated. The EL spectra and characteristics as well as structural parameters depend on the growth conditions and significantly modified after the annealing. Blue color emission with brightness of 10 cd m^− 2 under a sine wave excitation at 60 V and 5 kHz was obtained. The degradation behavior of the TFEL devices with ZnS:[Cu, Cl] films fabricated using an original non-vacuum methods of deposition and annealing is the same as that of commercial thin film phosphor.     

Novel quantum dots: Water-based CdTeSe/ZnS and YAG hybrid phosphor for white light-emitting diodes

Novel water-based core/shell CdTeSe/ZnS quantum dots (QDs) were synthesized by aqueous method. The CdTeSe/ZnS QDs were investigated by high resolution transmission electron microscopy, energy dispersive spectrometry, UV–vis absorption spectra, and photoluminescence spectrum. The as-prepared QDs capped with ZnS shell were spherical in shape with an excellent quantum yield of 16% and emitted bright yellow light. In addition, the CdTeSe/ZnS QDs can be excited by blue or near-UV region, which is an advantage over wavelength converters for white light-emitting diodes (LEDs). White LEDs based on CdTeSe/ZnS QDs, commercially known as Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce), and hybrid phosphor of CdTeSe/ZnS QDs and YAG:Ce, were fabricated. The luminescent properties of the resultant white LEDs were evaluated. The higher red-component in the emission spectrum from CdTeSe/ZnS QDs increased the color rendering index (CRI) value of the commercial YAG:Ce-based white LEDs, and the hybrid phosphor-based white LED had CIE-1993 color coordinate, color temperature, and CRI values of (0.3125, 0.2806), 7108 K and 83.3, respectively.     

Weighting the influence of TiO2 anatase/brookite ratio in TiO2–Ag porous nanocomposites on visible photocatalytic performances

Nanocomposites based on TiO₂ aerogel and Ag nanoparticles have been successfully obtained through different synthesis methods and their specific surface areas have been determined by N₂ sorption (BET method). The photocatalytic potential for salicylic acid degradation has been evaluated. It was found that under visible light irradiation, all synthesized nanocomposites exhibit higher photocatalytic activity than the commercially available Aeroxide P25. By correlating the structural parameters with the photocatalytic performances, it has been found that the Ag nanoparticles and brookite phase presence alongside the anatase play important roles on the visible photocatalysts behavior. For the Ag containing samples with mixed anatase–brookite phases, it has been observed that the visible photocatalytic performance decreases with the increase in brookite crystalline phase content. On the other hand, the addition of Ag nanoparticles results, as expected, in a clear enhancement of the visible photocatalytic activity.     

Preparation and characterization of zinc sulfide nanoparticles under high-gravity environment

Nanosized ZnS particles were prepared under high-gravity environment generated by the rotating packed bed reactor (RPBR) using zinc nitrate solution and hydrogen sulfide gas as raw materials. The effects of experimental conditions such as reactant concentration, reaction temperature, rotating speed of the RPBR and aging time, on the preparation of nanosized ZnS particles were investigated. A set of suitable operating parameters (the aging time of 48 h, concentration of zinc nitrate of 0.1 mol/l, reaction temperature of 45 °C and rotating speed of the RPBR of 1500-1800 rotation/min) for the preparation of nanosized ZnS were recommended. Under these optimum conditions, well-dispersed ZnS nanoparticles was obtained. The crystal structure, optical properties, size and morphology of the product were also characterized by XRD, UV-Vis spectrophotometer, and TEM, respectively. Results indicate that the prepared ZnS has a good absorption for light in the wavelength range of 200-330 nm. XRD analysis also shows the prepared ZnS is in a sphalerite crystal phase. The process has great potential of commercialization.     

Ag diffusion in ZnS thin films prepared by spray pyrolysis

ZnS thin films were deposited by spray pyrolysis method on glass substrates. Diffusion of Ag in ZnS thin films was performed in the temperature range 80-400 °C under a nitrogen atmosphere. The diffusion of Ag is determined with XRF, and the obtained concentration profile allows to calculate the diffusion coefficient. The temperature dependence of Ag diffusion coefficient is determined by the equation D = 8 × 10^− 9 exp(− 0.10 eV / kT). It was found that the as-grown undoped high resistive n-type ZnS thin films were converted to the p-type upon Ag doping with a slight increase in resistivity only by rapid thermal annealing at 400 °C in N₂ atmosphere. In addition, the band gap of the p-type film was decreased as compared with the undoped sample annealed under the same conditions. The results were attributed to the migration of Ag atoms in polycrystalline ZnS films by means of both along intergrain surfaces and intragrain accompanied by interaction with native point defect.     

Co-catalysis effect of different morphological facets of as prepared Ag nanostructures for the photocatalytic oxidation reaction by Ag–TiO2 aqueous slurry

This paper highlights the comparative co-catalytic efficiency of different shapes of prepared Ag nanoparticles of size much larger as well as smaller than titania for the Ag–TiO₂ photocatalysis. Quantum sized Ag nanospheres (4^_8 nm), nanorod (length 70–75 nm and width 30–38 nm), polygonal nanosphere (80–120 nm) and truncated triangles (side length 70–140 nm) are prepared by solvothermal process. The co-catalytic activities of these Ag nanostructures were investigated by mixing them with TiO₂ for the photocatalytic degradation of aqueous salicylic (0.5 mM) and benzoic acid (0.5 mM) under UV light (125 W-Hg arc, 10.4 mW cm⁻²) irradiation. The Ag co-catalysis effect imparted to TiO₂ follows as polygonal nanosphere > nanorod > truncated triangle > small nanosphere due to the formation of many Ag–TiO₂ interfaces by a single large-sized Ag nanoparticle than smaller one. As the surface coverage of Ag particles by TiO₂ decreases, the Ag–TiO₂ photoactivity is decreased accordingly. The efficient adsorption of salicylic acid to TiO₂ surface through –COOH and –OH groups render its higher photodegradation rate (1.8–2.7 × 10⁻² μmol min⁻¹) than benzoic acid (1.5–2.5 × 10⁻² μmol min⁻¹) having one chelating –COOH group. Zeta potential and conductance measurement of photoreaction mixture were carried out to investigate the ionic interaction-adsorption of reactant substrates over Ag–TiO₂ surface.     

Characterization of ZnS:Cu, Br electroluminescent phosphor prepared by new route

Synthesis of electroluminescent ZnS:Cu, Br phosphor by a number of routes has been presented along with their brightness-voltage, brightness-frequency, brightness-waveform and spectral energy distribution studies. The sample fired in N₂ atmosphere with aluminum and bromine shows predominantly green emission with a peak around 530 nm whereas the sample prepared under H₂S and HBr shows the broadest emission spectrum with multiple peaks. These peaks may arise out of different possible bands of copper, self-activated luminescence of ZnS and association of copper with some of the donor levels formed because of the higher reactivity of HBr. All the samples have been found to obey the relation B=B₀ exp.(−b/V^0.5) which has been discussed using bipolar tunnel emission model. The frequency variation of brightness is linear. Samples containing bromine show multiple secondary peaks indicating that bromine helps in formation of multiple shallow traps.     

Phoswich detectors combining doubly or triply ZnS(Ag), NE102A, BGO and/or NaI(Tl) scintillators for simultaneous counting of α, β and γ rays

Phoswich detectors for simultaneous counting of α, β and γ rays have been developed: ZnS(Ag)/Au Mylar/NE102A, ZnS(Ag)/Au Mylar/BGO and ZnS(Ag)/NaI(Tl) for α and β(γ) rays and ZnS(Ag)/Au Mylar/NE102A/BGO and ZnS(Ag)/NE102A/NaI(Tl) for α, β and γ rays. They were prepared by coupling a ZnS(Ag) film scintillator for α counting with a scintillator(s) for β and γ counting having different rise time. In order to adjust each component of pulse height within a given dynamic range, a sheet of Au-coated Mylar (Au Mylar) was used, if necessary, as an optical ND filter for lowering transmittance of scintillation of the ZnS(Ag). Characteristics of these phoswiches were examined by a technique of pulse-shape discrimination. Excellent discrimination among the radiations was attained and small tailings from each other peak were obtained for the prepared phoswiches.     

Luminescence response and CL degradation of combustion synthesized spherical SiO2:Ce nanophosphor

This study was aimed to systematically investigate the luminescence response of SiO₂:Ce³⁺ nanophosphors with different excitation sources. The powders were synthesized by using an urea assisted combustion method. SiO₂:Ce_1m% samples were also annealed at 1000 °C for 1 h in a charcoal environment to reduce incidental Ce⁴⁺ to partial Ce³⁺ ions. High resolution transmission electron microscopy (HRTEM) images of the as synthesized and annealed powder samples confirmed that the particles were spherical and in the size range of 3-8 nm in diameter. X-ray diffraction (XRD) and electron dispersion spectroscopy (EDS) results showed that the SiO₂ was crystalline and pure. Diffused reflectance, photoluminescence (PL) and cathodoluminescence (CL) results of the SiO₂:Ce³⁺ samples were obtained and compared with each other. The CL degradation and the surface reactions on the surface of the SiO₂:Ce³⁺ were studied with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). A clear improvement in the chemical stability of the SiO₂:Ce³⁺ annealed at 1000 °C were obtained.     

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.     

Assembly, characterization and swelling kinetics of Ag nanoparticles in PDMAA-g-PVA hydrogel networks

A series of poly(N,N-dimethylacrylamide)-g-poly(vinyl alcohol) (PDMAA-g-PVA) graft hydrogel networks were designed and prepared via a free radical polymerization route initiated by a PVA-(NH₄)₂Ce(NO₃)₆ redox reaction. Silver nanoparticles with high stability and good distribution behavior have been self-assembled by using these hydrogel networks as a nanoreactor and in situ reducing system. Meanwhile the PDMAA or PVA chains can efficiently act as stabilizing agents for the Ag nanoparticles in that Ag⁺ would form complex via oxygen atom and nitrogen atom, and form weak coordination bonds, thus astricting Ag⁺. The structure of the PDMAA-g-PVA/Ag was characterized by a Fourier transform infrared spectroscope (FTIR). The morphologies of pure PDMAA-g-PVA hydrogels and PDMAA-g-PVA/Ag nanocomposite ones were observed by a scanning electron microscopy (SEM) and transmission electron microscope (TEM). TEM micrographs revealed the presence of nearly spherical and well-separated Ag nanoparticles with diameters ranging from 10 to 20 nm, depending on their reduction routes. XRD results showed all relevant Bragg's reflection for crystal structure of Ag nanoparticles. UV–vis studies apparently showed the characteristic surface plasmon band at 410–440 nm for the existence of Ag nanoparticles within the hydrogel matrix. The swelling kinetics demonstrated that the transport mechanism belongs to non-Fickian mode for the PDMAA-g-PVA hydrogels and PDMAA-g-PVA/Ag nanocomposite ones. With increasing the DMAA proportion, the r₀ and S_∞ are enhanced for each system. The assembly of Ag nanoparticles and the swelling behavior may be controlled and modulated by means of the compositional ratios of PVA to DMAA and reduction systems.