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.     

A thermoluminescence study on the state of Cl in ZnS:Ag by electron beam

The degradation behavior of ZnS:Ag, Cl as a phosphor for CL by EB irradiation at 7 kV was examined by TL measurement. After EB irradiation, TL intensity decreased and the TL peak shifted to the lower temperature side. By comparing TL thermograms of mechanically damaged ZnS:Ag, Cl, ZnS:Cl with varying Cl concentration as well as ZnS:Ag, Al after EB irradiation, we conclude that the decrease in the effective concentration of Cl⁻, serving as active luminescence center, is responsible for the CL degradation of ZnS:Ag, Cl by EB irradiation.     

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.     

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.     

Dependence of optical and structural properties of ZnS and MgF2 multilayers as a function of the number of layers

In this paper, optical and structural properties of ZnS and MgF₂ multilayers grown by thermal evaporation are studied. Effects of annealing at different temperatures on samples with different number of layers are investigated. The maximum of reflection is shifted to different wavelengths, depending on the number of layers of the annealed samples. Using X-ray diffraction analysis, structural properties have been studied, and grain size and microstrain have been obtained by the Scherrer-Wilson formula, with grain sizes ranging from 10 nm to 22 nm for MgF₂ and from 0.9 nm to 210 nm for ZnS, and microstrain values from 2.5 × 10^− 3 to 3 × 10^− 3 for MgF₂, and from 1.2 × 10^− 3 to 2.6 × 10^− 3 for ZnS. Competition between crystallite size and microstrain is observed.     

Enhanced ultraviolet sensitivity of zinc oxide nanoparticle photoconductors by surface passivation

Zinc oxide nanoparticles were created by a top-down wet-chemical etching process and then coated with polyvinyl-alcohol (PVA), exhibiting sizes ranging from 10 to 120 nm with an average size approximately 80 nm. The PVA layer provides surface passivation of zinc oxide nanoparticles. As a result of PVA coating, enhancement in ultraviolet emission and suppression of parasitic green emission is observed. Photoconductors fabricated using the PVA coated zinc oxide nanoparticles exhibited a ratio of ultraviolet photo-generated current to dark current as high as 4.5 × 10⁴, 5 times better than that of the devices fabricated using uncoated ZnO nanoparticles.     

Radiative interface state study in CdSe/ZnS quantum dots covered by polymer

The paper presents the transformation of photoluminescence (PL) spectra of nonconjugated and bioconjugated core/shell CdSe/ZnS QDs covered by PEG polymer at the aging in ambient air. Studied QDs are characterized by the sizes: (i) 3.6-4.0 nm and color emission with the maxima at 560-565 nm (2.19-2.25 eV) and (ii) 5.2-5.3 nm and with emission at 605-610 nm (2.02-2.08 eV). The part of 565 nm CdSe/ZnS QDs has been bioconjugated to the mouse anti PSA (Prostate-Specific Antigen) antibodies and the part of 605 nm QDs has been bioconjugated to the antihuman IL10 (Interleukin 10) antibodies using the commercially available 565 nm and 605 nm QD conjugation kits. It is revealed that the aging process in ambient air has the very strong impact on PL spectra of nonconjugated core/shell CdSe/ZnS QDs covered with PEG polymer. The aging process relates to the polymer modification in ambient air that is accompanied by the three effects: (i) polymer transparency increasing for the emission of CdSe cores (2.03 or 2.20 eV), (ii) the intensity stimulation of high energy PL bands (2.37, 2.73 and 3.06 eV) related to the interface states at the ZnS/PEG polymer interface and (iii) the elastic strain modification in QD systems. The concentration of interface states at the ZnS/polymer interface increases at the aging of PEG polymer in ambient air.     

Structural and luminescence correlation of annealed Er-ZnO/Si thin films deposited by AACVD process

Er doped ZnO thin films have been synthesized from zinc acetates dihydrate (C₄H₆O₄Zn·2H₂O) and Erbium tris (2,2,6,6-tetramethyl-3,5-heptadionate) (Er(TMHD)₃) by aerosol assisted chemical vapor deposition AACVD atmospheric pressure technique. Films were deposited in the temperature range of [370–500 °C] on Si (1 1 1) substrate. Nano-disk shaped grains were grown on the top of the film surface. The morphology of the as-deposited films was found to be dependent on the substrate temperature. After annealing in air atmosphere, XRD patterns revealed a highly oriented c-axis Er:ZnO films with hexagonal wurtzite structure without any second phase. Under 488 nm excitation, the intra 4f–4f green emission (²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) gradually increased with increasing annealing temperature. Also, the local structure of Er changes to a pseudo-octahedral structure with C_4v symmetry. The ZnO film with 2.504 at.% Er³⁺ doping has the best crystalline structure and the best resolved PL spectra. Using 325 nm excitation, all the samples showed an ultraviolet emission centered at 380 nm originating from a near band EDGE emission and a broad band green emission centered at 520 nm from deep levels. The optical response was correlated with crystallinity of the synthesized thin films.     

Preparation,characterization, and photoluminescence study of PVA/ZnO nanocomposite films

ZnO nanoparticles with average diameter of 25 nm were synthesized by a modified sol–gel method and used in the preparation of (in wt.%) (100 − x) poly(vinyl alcohol) (PVA)/x ZnO nanocomposite films, with x = 0, 1, 2, 3, 4, and 5. The PVA/ZnO films were exposed to UV radiation for 96 h and their thermal, morphological, and spectroscopic properties were investigated. In inert atmosphere, the nanocomposite films showed lower thermal stability than the pure PVA film, and the calorimetric data suggest an interaction between PVA and ZnO in the nanocomposite films. Some crystalline phases could be seen in the films with ZnO, and a direct dependence on the ZnO concentration was also observed. The original structure of ZnO nanoparticles remained unaltered in the PVA matrix and they were uniformly distributed on the film surface. The roughness of the PVA film was not modified by the addition of ZnO; however, it increased after 96 h of UV irradiation, more significantly in the nanocomposite films. The films showed an absorption band centered at 370 nm and a broad emission band in the UV–vis region when excited at 325 nm.     

Synthesis of CdS hierarchical microspheres and their application in electrochemiluminescence sensing

CdS microspheres with hierarchical structures were prepared with sodium dodecylbenzenesulfonate (SDBS) as structure directing reagent. SEM analysis indicated that the CdS microspheres were constructed with CdS nanosheets, which were further built up with assembled CdS nanoparticles. Optical investigation showed that the obtained CdS microspheres have an UV-vis absorption at 445 nm and photoluminescence (PL) emissions at 498 and 573 nm. The CdS hierarchical microspheres were immobilized on a glassy carbon electrode and the electrochemiluminescence (ECL) properties were investigated. The first application to sensing H₂O₂ was studied based on ECL from CdS hierarchical microspheres. A linear relation between the ECL intensity and H₂O₂ concentration, I = 2.4212 + 2.1713 c, was obtained with a detection limit of 1 × 10⁻⁸ mol·L^− 1.     

Facile template-free fabrication of olive-like ZnO nanoparticles and their photoluminescence properties

A facile template-free solvothermal approach was applied to synthesize olive-like ZnO nanoparticles with an average diameter of about 300 nm and an average length of about 600 nm. XRD, TEM, SEM, SAED, EDX and PL spectra were employed to characterize the crystal phase, morphologies, the chemical compositions, and optical properties of the ZnO nanostructure. The experimental results showed the as-obtained ZnO was single-crystalline nanostructure and the concentration of CH₃COO⁻ solution played a key role in controlling the morphology of ZnO. The growth mechanism of ZnO was tentatively investigated. Besides, the olive-like ZnO nanoparticles exhibit a very strong ultraviolet emission centered at 383 nm and a weak green luminescence emission at around 522 nm.     

Preparation of (ZnO)1−x(GaN)x:Mn powder and its photoluminescence properties

(ZnO)_1−x(GaN)_x:Mn²⁺ powder was prepared by a conventional solid-state reaction under an NH₃ gas flow. The sample preparation conditions including the mixing ratio of the raw materials, the annealing temperature, and the annealing time were varied. The crystallinity and the photoluminescence (PL) intensity of this fluorescent material were improved by increasing the amount of ZnO and by increasing the annealing time, and no changes was observed in the PL wavelength. The crystallinity of the samples was enhanced and the PL intensity increased markedly at annealing temperatures of 700 °C and 800 °C, respectively. Moreover, it was clarified that the sample could be synthesized at annealing temperatures of above about 650 °C.     

Optical and electrical properties of ZnO films prepared by URT-IP method

Optical and electrical properties were studied on thin polycrystalline ZnO films (200-nm thick) deposited on glass substrates at 200 °C by a DC-arc ion plating method (URamoto-Tanaka-type ion plating method). Effects of the oxygen flow rate (OFR) on film properties were examined. The resistivity of undoped films changed from 4.2×10⁻³ to 9.6×10⁻¹ Ω cm, corresponding to the carrier concentration of 1.0×10²⁰-1.2×10¹⁸ cm⁻³, depending on the increase in OFR from 0 to 40 sccm. The Hall mobility tends to be the maximum value of 28 cm² (V s)⁻¹ at OFR of 10 sccm. Photoluminescence (PL) spectra exhibited a dominant near-band-edge (NBE) emission together with weak PL bands at 2.2 and 3.2 eV. Intensity of NBE was maximum at OFR of 10 sccm. Intensity of the PL band at 2.2 eV increased with increase in OFR. As a result of Ga-doping, the resistivity decreased and the carrier concentration increased by one order of magnitude. The optical transmittance was more than 90% in 400-1200 nm. The ZnO:Ga (3 and 4 wt.% Ga-doped) thin films with the lowest resistivity of 2.6×10⁻⁴ Ω cm, the highest mobility of 25 cm² (V s)⁻¹, and the highest PL intensity were obtained at OFR of 10 sccm. Further increase of OFR led to the decrease in both mobility and PL intensity.     

A new fluorescent film sensor for Pb(II) ions developed by simulating bio-mineralization process synthesizing of ZnS/CS nanocomposite

Chitosan/zinc sulfide (CS/ZnS) nano-composite films have been prepared by simulating bio-mineralization process. Factors affecting the hydrothermal stability and fluorescence properties of the films have been studied. Furthermore, the sensing properties of nano-composite films to lead ions have been systematically investigated. SEM and TEM observations showed that the size of ZnS particles is 70 nm, and the particles are evenly distributed within the CS films. The fluorescence emission of the nano-composite films indicates that the sizes of real fluorescing ZnS particles are less than 20 nm. This suggests that ZnS particles observed via SEM and TEM may be aggregates of smaller ZnS particles, and the smaller particles may be separated by the organics. The fluorescence emission (363 nm) of the nano-composite films is very sensitive to the presence of Pb ions. C_(Pb²⁺₎ increased from 0 to 664.2 mg L⁻¹ increases the emission dramatically. The emission is hardly affected by common ions in water, except for the iron ions. The films may be developed as excellent sensing films for Pb ions in water.     

Structure and photoluminescence properties of ZnS nanowires sheathed with SnO2 by atomic layer deposition

Influence of the thermal annealing atmosphere on the photoluminescence properties of ZnS-core/SnO₂-shell coaxial nanowires was investigated. ZnS nanowires were synthesized by a two-step process: the thermal evaporation of ZnS powders and the atomic layer deposition of SnO₂. Transmission electron microscopy and X-ray diffraction analyses reveal that two crystalline ZnS phases: one with a zinc blende structure and the other with an wurtzite structure coexist in the cores whereas the SnO₂ cores in the as-prepared coaxial nanowires are amorphous. The SnO₂ shells are found to be crystallized by thermal annealing. Photoluminescence (PL) measurements at room temperature show that the green emission of the ZnS/SnO₂ coaxial nanowires is enhanced in intensity by thermal annealing regardless of the annealing atmosphere. The PL emission is more significantly enhanced in intensity by annealing in a reducing atmosphere than in an oxidative atmosphere since Au_Zn ⁻ is more easily generated in the ZnS cores in the former atmosphere.     

Synthesis and characterization of photoluminescent cerium-doped yttrium aluminum garnet

Powder phosphor yttrium aluminum garnet (YAG), doped with trivalent cerium (Ce³⁺) is synthesized by sol-gel method. The formation of YAG and YAG:Ce (cerium-doped yttrium aluminum garnet) was investigated by means of X-ray diffraction (XRD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were also used. The purified crystalline phases of YAG and YAG:Ce were obtained at 1000 °C. The maximum average grain size is about 20-23 nm for undoped samples and 28-34 nm for doped samples. The crystalline YAG:Ce emission shows one peak in the range 480-535 nm with the maximum near 520 nm. Photoluminescence (PL) intensity of 5d → 4f transition of Ce³⁺ increased with increasing annealing temperature. With increasing the concentration of Ce³⁺, the photoluminescence peak shifts towards the red region.     

Dependence of photoluminescence (PL) emission intensity on Eu and ZnO concentrations in Y2O3:Eu and ZnO·Y2O3:Eu nanophosphors

Y₂O₃:Eu³⁺ and ZnO·Y₂O₃:Eu³⁺ nanophosphor powders with different concentrations of Eu³⁺ ions were synthesized by a sol-gel method and their luminescence properties were investigated. The red photoluminescence (PL) from Eu³⁺ ions with the main emission peak at 612 nm was observed to increase with Eu³⁺ concentration from 0.25 to 0.75 mol% and decreased notably when the concentration was increased to 1 mol%. The decrease in the PL intensity at higher Eu³⁺ concentrations can be associated with concentration quenching effects. The red emission at 612 nm was shown to increase considerable when ZnO nanoparticles were incorporated in Y₂O₃:Eu³⁺ while green emission from ZnO was suppressed. The increase is attributed to energy transfer from ZnO to Eu³⁺.     

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.%.     

Structural, optical, and nonlinear optical absorption/refraction studies of the manganese nanoparticles prepared by laser ablation in ethanol

The structural, optical, and nonlinear optical properties of the manganese nanoparticles prepared by laser ablation in various liquids were investigated using the 532 and 1064 nm, 50 ps laser pulses. The TEM and spectral measurements showed temporal dynamics of size distribution of Mn nanoparticles in solutions. The nonlinear absorption (β = 2 × 10⁻¹⁰ and 4 × 10⁻¹¹ cm W⁻¹) and positive nonlinear refraction (γ = 8 × 10⁻¹⁵ and 2 × 10⁻¹⁴ cm² W⁻¹) of picosecond radiation were observed in the Mn colloidal suspensions using the 1064 and 532 nm radiation, respectively     

Low temperature synthesis of h-BN nanoflakes

Boron nitride (BN) with flake-like morphology has been synthesized by reacting powder H₃BO₃, Mg and NH₄Cl in an autoclave at 600 °C for 10 h. X-ray diffraction (XRD) patterns show the sample has hexagonal phase with lattice parameters a = 2.506 and c = 6.692 Å. Transmission electron microscopy (TEM) and field emission scanning electron (FE-SEM) indicate the as-synthesized product is pure flake with a mean size of about 100 nm in thickness and 600 nm in width length. X-ray photoelectron spectra (XPS) give an average B/N atomic ratio of 0.98:1. Fourier transformation infrared spectroscopy (FTIR) has a strong B-N absorption at 1376 cm^− 1 and 814 cm^− 1.