Energy transfer from organic surface adsorbate-polyvinyl pyrrolidone molecules to luminescent centers in ZnS nanocrystals

Multi-colour emitting doped ZnS nanocrystals surface capped with pyridine (P-ZnS) or polyvinyl pyrrolidone (PVP-ZnS) have been synthesized by wet chemical methods. The photoluminescence studies show that the dopant related emission from P-ZnS nanocrystals are caused by the energy transfer from band-to-band excitation of the host lattice. However, in the case of PVP capped ZnS, considerable enhancement in the emission intensity was observed and the corresponding excitation spectra appeared dramatically broadened due to the presence of multiple excitation bands with peak maxima at 235, 253, 260, 275, and 310 nm. The bands from 235 to 275 nm are assigned to the electronic transitions in the chemisorbed PVP molecules whereas the excitation maximum around 310 nm corresponds to the band-to-band transition within the nanocrystalline ZnS host. The presence of PVP related energy bands in the excitation spectrum indicates the process of energy transfer from the surface adsorbed PVP molecules to dopant centers in ZnS nanocrystals. This study brings out a heterogeneous sensitizer-activator relation between organic surface adsorbate and doped semiconducting nanocrystals.     

Study of optical and thermal properties in nickel doped ZnS nanoparticles using surfactants

The presence of surfactants polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), sodium hexameta polyphosphate (SHMP) and tri-octyl phosphine oxide (TOPO) on the surface of Ni²⁺ doped ZnS (ZnS:Ni²⁺) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped ZnS:Ni²⁺ nanoparticles were investigated using UV–visible (UV–Vis) absorption and photoluminescence (PL) techniques. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc sulfide. The effect of the optical properties in colloidal form (wet) and dry samples were investigated. Enhanced PL emission was observed for the dry samples at 80 °C. Thermal properties of the ZnS:Ni²⁺ was also studied using thermo gravimetric-differential thermal analysis (TG-DTA), Fourier transform infra-red spectrometer (FT-IR) and X-ray diffraction (XRD). The results are presented and discussed.     

Photoluminescence and optical characterization of CdS nanoparticles prepared by solid-state method at low temperature

The photoluminescence (PL) and optical properties of CdS nanoparticles prepared by the solid-state method at low temperature have been discussed. The effects of NaCl and anionic surfactant SDBS (sodium dodecylbenzene sulfonate) on the luminescent properties of CdS nanophosphors prepared using this method, without the inert gas or the H₂S environment, were studied separately. The synthesized products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscope (FESEM), and energy dispersive X-ray spectroscopy (EDAX). UV–VIS absorption and PL spectra were also studied. XRD studies confirmed the single-phase formation of CdS nanoparticles. TEM micrograph revealed the formation of nearly spherical nanoparticles with a diameter of 2.5 nm. The PL emission for the CdS shows the main peak at 560 nm with a shoulder at 624 nm, with an increase in the PL intensity after the addition of SDBS. The effect of Mn doping on PL intensity has also been investigated. The PL spectra show that the emission intensity decreases as the dopant concentration increases.     

Influences of capping molecules on optical properties of nanocrystalline ZnS:Cu

ZnS:Cu nanocrystals capped with different capping molecules have been successfully synthesized by a simple aqueous method. The prepared nanocrystals were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive analysis by X-rays (EDAX). The surface characterization of the nanocrystals was done by FTIR spectroscopy. The effect of capping agents on absorption and photoluminescence (PL) spectra of the ZnS:Cu nanocrystals was studied. A blue shift of the absorption peaks was observed and attributed to a quantum confinement effect, which increases the band gap energy. The photoluminescence spectra of the capped ZnS:Cu nanocrystals showed a broad peak in the range of 460–480 nm. The intensity of the PL spectra strongly depended on the capping agents.     

Photophysical and photoluminescence properties of co-activated ZnS:Cu,Mn phosphors

ZnS:Cu,Mn phosphors were prepared by conventional solid state reaction with the aid of NaCl-MgCl₂ flux at 900 °C. The samples were characterized by X-ray powder diffraction, UV-vis absorbance spectra and photoluminescence spectra. All samples possess cubic structure. Cu has a much stronger effect on the absorption property of ZnS than Mn. Incorporation of Mn into ZnS host only slightly enhances the light absorption, while addition of Cu remarkably increases the ability of absorption due to ground state Cu⁺ absorption. The emission spectra of the ZnS:Cu,Mn phosphors consist of three bands centered at about 452, 520 and 580 nm, respectively. Introduction of Mn significantly quenches the green luminescence of ZnS:Cu. The excitation energy absorbed by Cu is efficiently transferred to Mn activators non-radiatively and the Mn luminescence can be sensitized by Cu behaving as a sensitizer (energy donor).     

Synthesis and optical characterization of PVP and SHMP-encapsulated Mn-doped ZnS nanocrystals

Zinc sulfide semiconductor nanocrystals doped Mn²⁺ have been synthesized via a solution-based method utilizing optimum dopant concentration (4%) and employing polyvinyl pyrrolidone (PVP) and sodium hexametapolyphosphate (SHMP) as capping agents. UV-vis absorbance spectra for all of the synthesized nanocrystals show an exitonic peak at around 310 nm. The particle size and morphology were characterized by scanning electron microscopy (SEM), FT-IR, X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectrum (PL). Diffraction data confirmed that the crystallite size is around 3-5 nm. Room temperature photoluminescence (PL) spectrum for the bare ZnS sample shows a strong band at ∼445 nm. The uncapped and capped(SHMP, PVP) ZnS:Mn²⁺ samples show a strong and broad band in the ∼580-585 nm range.     

Effect of Mn doping on the structural and optical properties of sol-gel derived ZnO nanoparticles

Un-doped and Mn-doped ZnO nanoparticles were successfully synthesized in an ethanolic solution by using a sol-gel method. Material properties of the samples dependence on preparation conditions and Mn concentrations were investigated while other parameters were controlled to ensure reproducibility. It was observed that the structural properties, particle size, band gap, photoluminescence intensity and wavelength of maximum intensity were influenced by the amount of Mn ions present in the precursor. The XRD spectra for ZnO nanoparticles show the entire peaks corresponding to the various planes of wurtzite ZnO, indicating a single phase. The diffraction peaks of doped samples are slightly shifted to lower angles with an increase in the Mn ion concentration, signifying the expansion of the lattice constants and increase in the band gap of ZnO. All the samples show the absorption in the visible region. The absorbance spectra show that the excitonic absorption peak shifts towards the lower wavelength side with the Mn-doped ZnO nanoparticles. The PL spectra of undoped ZnO consist of UV emission at 388 nm and broad visible emission at 560 nm with varying relative peak intensities. The doping of ZnO with Mn quenches significantly the green emission while UV luminescence is slightly affected.     

Preparation and luminescent characteristic of Li3NbO4 nanophosphor

Synthesis and luminescence properties of Li₃NbO₄ oxides by the sol-gel process were investigated. The products were characterized by the X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and absorption spectra. The PL spectra excited at 247 nm have a broad and strong blue emission band maximum at 376 nm, corresponding to the self-activated luminescence of the niobate octahedra group [NbO₆]⁷⁻. The optical absorption spectra of the samples sintered at temperatures of 600 and 700 °C exhibited the band-gap energies of 4.0 and 4.08 eV.     

Structural and optical characterization of ZnS nanoparticles co-doped with Mn and Te

Nanoparticles of Zinc sulfide co-doped with equal atomic percentages of Mn and Te (5, 10 and 15 at%) were synthesized for the first time by chemical co-precipitation method. Thiophenol was used to passivate the surface of the particles. The as-prepared samples were amorphous in nature and nano-crystallinity was induced after calcining at 300 °C/2 h. The nanoparticles were characterized by EDAX, XRD, TEM, optical absorption and PL studies. EDAX spectra revealed only minor deviations of the dopant concentrations from the target compositions. The nanoparticles showed cubic structure. The particle size estimated from XRD/TEM was in the range 3–5 nm. Optical absorption studies showed a blue-shift of the fundamental absorption edge with respect to that of bulk ZnS. PL spectra showed emission in the red region with composition dependent emission wavelength. ZnS nanoparticles doped with Mn (5 and 10 at%) were also synthesized and characterized for comparison.     

树形分子包覆的ZnS量子点对潜指纹的荧光标记成像研究

在Zn2+离子与聚酰胺-胺(PAMAM)树形分子配位的基础上,制备了稳定的PAMAM树形分子包覆的ZnS量子点(quantum dots,QDs),并用紫外-可见吸收光谱(UV-Vis)和荧光发射光谱进行了表征。结果表明,Zn2+离子能与PAMAM树形分子发生配位络合作用,且饱和配位时间为6h;在波长365nm紫外光的激发下,PAMAM树形分子包覆的ZnS量子点发射出明亮的蓝色荧光,荧光发射峰约位于450nm。最后,将得到的PAMAM树形分子包覆的ZnS量子点纳米复合材料应用于锡纸上潜指纹的荧光标记成像研究,发现指纹可以被清晰识别,呈现明亮的蓝色荧光指纹。     

高场电致发光过程的动力学分析

本文通过对交流(ZnS:Mn,Cu)和直流(ZnS:Mo,Cu(Cu))两种不同结构的粉末发光材料的发光光谱,时间分辨发光光谱,电流波形,发光亮度波形,发光衰减以及发光强度与掺杂浓度的关系等方面的研究,对Mn和Cu这两种不同类型的发光中心的高场电致发光过程进行了分析,并用一个统一的模型对两种不同类塑的发光中心建立了发光动力学方程,由此解得Mn中心和Cu中心的发光强度随时间的变化规律表达式,它们分别包括了Mn中心和Cu中心发光亮度波形的所有情形。我们从动力学分析出发,找到了影响Cu中心和Mn中心发光强度的主要因素,并从理论上预言了提高发光强度的可能途径。     

Green Emitting Cerium Doped CaS Whiskers Grown by Solid State Diffusion Method

Undoped and cerium doped Calcium sulfide (CaS) phosphors were synthesized using solid state diffusion method. The X-ray diffraction pattern revealed that both undoped and doped CaS crystallites have cubic structure with average crystallite size varying from 20 to 30 nm. Scanning electron micrographs indicated that Ce doped CaS phosphors were composed of whiskers with different dimensions and orientations. The optical properties of undoped and Ce doped particles were characterized using Photoluminescence (PL) and UV-Vis absorption spectroscopy. The PL emission spectrum of cerium doped CaS phosphors for an excitation wavelength 465 nm showed a main peak at 500 nm and a shoulder peak at 556 nm due to 5d?→?4f transition in Ce³⁺ ions. The variation of PL intensity with cerium concentration was investigated and the maximum PL intensity was obtained for a doping concentration of 3 wt.%. The optical band gap of the samples was estimated from the diffuse reflectance spectrum and was found to increase with increase in cerium concentration. The enhanced optical properties of these phosphors can be exploited in various optoelectronic devices including displays and bioimaging techniques.     

Study of steady state and time resolved photoluminescence of thiol capped CdS nanocrystalline powders dispersed in N,N-dimethylformamide

The microwave (MW) assisted synthesis of thiol capped cadmium sulfide (CdS) nanocrystallites/quantum dots (QDs) was performed through the reaction of cadmium acetate with thiourea in N,N-dimethylformamide (DMF) by keeping the MW irradiation time fixed (40 s) in the presence of a thiol containing capping agent. Three capping agents, namely, benzyl mercaptan (BM), 1-butanethiol (BT) and 2-mercaptoethanol (ME) were used. The concentration of the precursors was varied to check the change in the average size of the thiol capped CdS nanocrystals formed. The nanocrystallites were characterized by usual procedure. The UV-vis absorption spectra and the photoluminescence (PL) spectra of the CdS nanocrystalline powders dispersed in DMF were studied. It was observed that with increase in concentration of the capping agent (BM), there is a shift in the nature of emission (PL) from trap associated PL to the band edge luminescence in the case of BM capped CdS nanocrystalline powders dispersed in DMF possibly due to better surface passivation. The relative PL quantum yield of the thiol capped CdS nanocrystalline powders dispersed in DMF was calculated under various experimental conditions. Time-correlated single-photon counting experiments were performed to study the time-resolved photoluminescence of the CdS nanocrystalline powders dispersed in DMF. The observed emission decay profiles have been simulated using the multiexponential model. The emission decay profiles for thiol capped CdS nanocrystalline powders dispersed in DMF depend on the nature of the capping agents (thiols) used to passivate the CdS nanocrystallites. The time resolved PL studies show that the average values of PL lifetime are related to the size and size distribution of the prepared thiol capped CdS nanocrystallites.     

水热法制备ZnS:Cu,Tm超细X射线发光粉

研究了水热法合成的ZnS: Cu,Tm超细X射线发光粉及其光致发光(PL)和X射线激发发光(X-ray excited luminescence,XEL)光谱特性.200 ℃水热处理12 h直接合成样品的纳米晶粒径约15 nm,尺寸分布窄,分散性好,具有纯立方相的类球形结构.氩气保护下900 ℃退火1 h后的样品存在一定的团聚,但团聚后尺寸为200—600 nm,为超细X射线发光粉,此时样品为纯六方相的类球形为主的结构.所有样品的PL和XEL光谱均为宽带谱.水热法直接合成样品的XEL强度最强时,样品的Cu/Zn,Tm/Cu比值分别为3×10^-4和2.在此比值条件下,900 ℃退火1 h样品的XEL发光最强,此时其两个峰值分别位于453,525 nm.发光强度增强的同时粒径很小,对提高成像系统分辨率非常有意义.通过比较PL光谱与XEL光谱特性,讨论了PL和XEL光谱的发光机理和其不同的激发机理. 关键词： ZnS:Cu Tm 水热法 X射线激发发光     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Absorption and photoluminescence properties of silver clusters in SiO<Subscript>2</Subscript> matrix

Absorption and luminescence properties of silver nanoclusters embedded in SiO₂ matrixes were studied experimentally. Thin SiO₂ films with different amount of silver were produced by co-deposition of Ag and SiO₂ onto the silica substrates in vacuum. The thus obtained films possess three peaks in absorption spectra at 297, 329 and 401 nm and two peaks in luminescence spectra at about 500 and 650 nm. We ascribed these spectral features to silver nanoclusters of different sizes that present in the film. Thermal annealing transforms both absorption and emission spectra of the films. Lager clusters that are formed after annealing possess one absorption band at 350–450 nm and one luminescence band at 510 nm. The luminescence was observed only in samples with the silver content of less than 2.2%. Quenching of the luminescence in samples with higher concentration of silver is due to the presence of larger particles with plasmonic properties.     

Spectroscopy of Nickel-Doped Zinc Sulfide Nanoparticles

ABSTRACT

In the present study, Zn_1?xNi_xS (x = 0.0–0.8 mol%) nanoparticles were prepared through the chemical route and the synthesis involved the mixing and drying of zinc acetate and sodium sulphide in an appropriate ratio with the addition of Ni²⁺ at a proper concentration. The structural and spectroscopic studies are investigated by X-ray diffraction (XRD), absorption spectra, emission and excitation spectra, and Raman spectra. Compared with that of the pristine materials, the absorption band-edge demonstrates an apparently blue shift, which is attributed to the quantum size effect. The average particle size of ZnS nanoparticles is in the range of 2–4 nm deduced from the XRD line broadening. Excited at about 330 nm, a blue emission band at 425 nm can be observed, which corresponds to Ni²⁺ luminescent center; this result is consistent with the postulation that Ni²⁺ replaced the Zn²⁺ ions in the lattice of ZnS nanocrystals. Excitation spectra also confirm the above postulation. The effect of different concentrations of nickel is also studied by Raman spectra.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

A comparative study of conventional type II and inverted core–shell nanostructures based on CdSe and ZnS

The objective of this work is to investigate structural, morphological and optical properties of conventional CdSe/ZnS core–shell and inverted ZnS/CdSe core–shell nanostructures for opto-electronic device applications. For this purpose both nanostructures were synthesized using chemical bath deposition technique in thin film form. The structural properties were studied using X-ray diffraction technique with Rietveld refinement and transmission electron microscopy (TEM). The surface morphology of synthesized thin film was illustrated in the form 2D and 3D images using atomic force microscopy (AFM). The optical properties were explained using UV–Vis absorption spectroscopy and photo luminescence (PL) spectroscopy in in situ monitoring process. A comparison of estimated particle size from XRD, high resolution AFM and TEM images was resulted in good agreement as 2.1, 2.4 and 2.1 nm respectively for conventional CdSe/ZnS core–shell and as 2.5, 2.5 and 2.2 nm respectively for inverted ZnS/CdSe core–shell nanostructures.     

Structure and photoluminescence properties of ZnS films grown on porous Si substrates

ZnS films were deposited on porous silicon (PS) substrates with different porosities. With the increase of PS substrate porosity, the XRD diffraction peak intensity decreases and the surface morphology of the ZnS films becomes rougher. Voids appear in the films, due to the increased roughness of PS structure. The photoluminescence (PL) spectra of the samples before and after deposition of ZnS were measured to study the effect of substrate porosity on the luminescence properties of ZnS/PS composites. As-prepared PS substrates emit strong red light. The red PL peak of PS after deposition of ZnS shows an obvious blueshift. As PS substrate porosity increases, the trend of blueshift increases. A green emission at about 550 nm was also observed when the porosity of PS increased, which is ascribed to the defect-center luminescence of ZnS. The effect of annealing time on the structural and luminescence properties of ZnS/PS composites were also studied. With the increase of annealing time, the XRD diffraction peak intensity and the self-activated luminescence intensity of ZnS increase, and, the surface morphology of the ZnS films becomes smooth and compact. However, the red emission intensity of PS decreases, which was associated with a redshift. White light emission was obtained by combining the luminescence of ZnS with the luminescence of PS.