Thermal Characteristics of PVA-PANI-ZnS Nanocomposite Film Synthesized by Gamma Irradiation Method

Gamma irradiation is employed for in situ preparation of PVA-PANI-ZnS nanocomposite. The irradiation dose is varied from 10 to 40 kGy at 10 kGy intervals. The XRD result confirms the formation of crystalline phases corresponding to ZnS nanoparticles, PVA and PANI. Field emission scanning electron microscopy shows the formation of agglomerated PANI along the PVA backbone, within which the ZnS nanoparticles are dispersed.UV-visible spectroscopy is conducted to measure the transmittance spectra of samples revealing the electronic absorption characteristics of ZnS and PANI nanoparticles. Photo-acoustic(PA) setup is installed to investigate the thermal properties of samples. The PA spectroscopy indicates a high value of thermal diffusivity for samples due to the presence of ZnS and PANI nanoparticles. Moreover, at higher doses, the more polymerization and formation of PANI and ZnS nanoparticles result in enhancement of thermal diffusivity.     

Two-photon spectroscopy and analysis with a white-light continuum probe

We present a powerful experimental tool and analysis for characterization of two-photon absorption (2PA) spectra. We demonstrate this method with ZnS and then apply it to organic dyes in solution. We also compare the results with those from other methods such as two-photon fluorescence spectroscopy. This femtosecond pump-probe method uses a white-light continuum (WLC) as the probe to produce a nondegenerate 2PA spectrum. The extreme chirp of the WLC requires that transmittance data be collected over a range of temporal delays between pump and probe pulses. These data then need to be corrected for the effects of this chirp as well as for the temporal walk-off of the pulses in the sample that result from the frequency nondegenerate nature of the experiment. We present a simple analytic solution for the transmitted fluence through the sample, which is applicable for most practical cases.     

Cr2+: ZnS和Fe2+: ZnS光谱特性的比较研究

基于密度泛函理论和投影平面波方法,采用第一性原理对比分析了Cr2+: ZnS和Fe2+: ZnS 的电子结构和光学性能。晶体中二价掺杂离子的态密度、能带结构和几何优化由广义梯度近似的PBE描述。Cr2+: ZnS和Fe2+: ZnS的近中红外光谱表明,特征吸收来自于局域激发的d和p-d杂化轨道之间的跃迁,Fe2+: ZnS的中心跃迁能量比Cr2+: ZnS的要低,红移0.34 eV;分别制备了Cr2+: ZnS和Fe2+: ZnS晶体,并测得了Cr2+: ZnS和Fe2+: ZnS的吸收光谱,证实了Fe2+: ZnS的特征吸收峰较Cr2+: ZnS红移0.34 eV。     

Cr~(2+):ZnS和Fe~(2+):ZnS光谱特性的比较研究

基于密度泛函理论和投影平面波方法,采用第一性原理对比分析了Cr2+:ZnS和Fe2+:ZnS的电子结构和光学性能。晶体中二价掺杂离子的态密度、能带结构和几何优化由广义梯度近似的PBE描述。Cr2+:ZnS和Fe2+:ZnS的近中红外光谱表明,特征吸收来自于局域激发的d和p-d杂化轨道之间的跃迁,Fe2+:ZnS的中心跃迁能量比Cr2+:ZnS的要低,红移0.34eV;分别制备了Cr2+:ZnS和Fe2+:ZnS晶体,并测得了Cr2+:ZnS和Fe2+:ZnS的吸收光谱,证实了Fe2+:ZnS的特征吸收峰较Cr2+:ZnS红移0.34eV。     

用ESR研究ZnS微晶的相变

在ZnS和ZnS:Cu磷光体微晶中,共掺杂痕量的Mn2+,通过对ZnS晶体中的Mn2+离子的电子自旋共振(下面简写为ESR)超精细谱的监测,可以研究ZnS和ZnS:Cu微晶随制备时的煅烧温度升高引起的从立方相(β相)到六角相(α相)的相变。痕量Mn2+是一种灵敏的结构相变顺磁探针。     

The structure and photoluminescence properties of TiO<Subscript>2</Subscript>-coated ZnS nanowires

The structure and photoluminescence properties of TiO₂-coated ZnS nanowires were investigated. ZnS nanowires were synthesized by thermal evaporation of ZnS powder and then coated with TiO₂ by using the metal organic chemical vapor deposition (MOCVD) technique. We performed scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, and photoluminescence (PL) spectroscopy to characterize the as-synthesized and TiO₂-coated ZnS nanowires. TEM and XRD analyses revealed that the ZnS core and the TiO₂ coatings had crystalline zinc blende and crystalline anatase structures, respectively. PL measurement at room temperature showed that the as-synthesized ZnS nanowires had two emissions: a blue emission centered in the range from 430 to 440 nm and a green emission at around 515 nm. The green emission was found to be dominant in the ZnS nanowires coated with TiO₂ by MOCVD at 350°C for one or more hours, while the blue emission was dominant in the as-synthesized ZnS nanowires. Also the mechanisms of the emissions were discussed.     

Optical properties of annealed Mn-doped ZnS nanoparticles

Cysteine stabilized ZnS and Mn²⁺-doped ZnS nanoparticles were synthesized by a wet chemical route. Using the ZnS:Mn²⁺ nanoparticles as seeds, silica-coated ZnS (ZnS@Si) and ZnS:Mn²⁺ (ZnS:Mn²⁺@Si) nanocomposites were formed in water by hydrolysis and condensation of tetramethoxyorthosilicate (TMOS). The influence of annealing in air, formier gas, and argon at 200-1000 °C on the chemical stability of ZnS@Si and ZnS:Mn²⁺@Si nanoparticles with and without silica shell was examined. Silica-coated nanoparticles showed an improved thermal stability over uncoated particles, which underwent a thermal combustion at 400 °C. The emission of the ZnS@Si and ZnS:Mn²⁺@Si passed through a minimum in photoluminescence intensity when annealed at 600 °C. Upon annealing at higher temperatures, ZnS@Si conserved the typical emission centered at 450 nm (blue). ZnS:Mn²⁺@Si yielded different high intensity emissions when heated to 800 °C depending on the gas employed. Emissions due to the Mn²⁺ at 530 nm (green; Zn₂SiO₄:Mn²⁺), 580 nm (orange; ZnS:Mn²⁺@Si), and 630 nm (red; ZnS:Mn²⁺@Si) were obtained. Therefore, with a single starting product a set of different colors was produced by adjusting the atmosphere wherein the powder is heated.     

二价铕激活的ZnS磷光体的发光

本文详细描述了ZnS:Eu2+磷光体的合成及光致发光性能。首次报导了这种发光材料的特殊长余辉特性。作者测量了热释发光光谱、不同温度下的发射特性的变化及荧光的激发、发射衰减时间,提出两类缔合Eu中心的模型。用不同的缔合Eu中心较好地解释了它的光谱特性及长余辉现象,认为光谱的两个发射带来自不同的缔合Eu中心,即550nm发射带对与ZnS导带电子陷阱相缔合的Eu中心有关,650nm带来自与电子陷阱和空穴陷阱缔合的Eu中心。发射的余辉主要与导带中某种电源电子陷阱存在有关。此外,本文还对与应用有关的阴极射线发光性能进行了报导。     

ZnS:Tm薄膜电致发光的激发过程

利用电子束蒸发方法制得ITO-Y2O3-ZnS:Tm3+-Y2O3-Al结构的薄膜可以得到蓝色电致发光.本文首次报导了ZnS:Tm3+薄膜与ZnS:Er3+、ZnS:Tb3+薄膜电致发光的激发过程有所不同.Tm3+离子的激发可以通过某些杂质中心到Tm3+离子的能量传递来实现.     

Ag或Cu离子注入形成的ZnS MIS结及其蓝色电致发光

本文叙述了在室温下用能量为70~100keV,剂量为1~3×1015cm-2的Ag或Cu离子注入到低阻ZnS晶体中,经N2气流350℃下退火处理,并用扫描电镜观测晶片断面的反射电子像(REI),吸收电子像(AEI)和二次电子像(5EI),发现了经离子注入的ZnS晶片表面存在一个厚约1μ的绝缘层,还根据对MIS结C-V特性测量,计算了二极管Ⅰ层的厚度为1.1μ,它与用扫描电镜观测的结果一致.文中还测量了ZnS:Ag(或Cu)MIS二极管在正向电压下的发光光谱,根据谱峰位置表明发光分别起源于Ag(或Cu)发光中心.在室温下用肉眼观察二者皆为蓝色电致发光.     

Controlled extracellular biosynthesis of ZnS quantum dots by sulphate reduction bacteria in the presence of hydroxypropyl starch as a mediator

Metal sulphide quantum dots (QDs) have broad applications. Sulphate-reducing bacteria (SRB) have been recognized as synthesizers of metal sulphides, with the characteristics of a high-production efficiency and easy product harvest. However, SRB are incapable of synthesizing metal sulphide QDs. In the present study, cheap hydroxypropyl starch (HPS) was used to assist SRB in manufacturing the ZnS QDs. The results exhibited that the HPS accelerated the growth of SRB and reduction of SO₄ ²⁺ into S^2?, while it blocked the precipitation between S^2? and Zn²⁺ to control the nucleation and growth of ZnS, resulting in the formation of ZnS QDs. When the HPS concentration increased from 0.2 to 1.6 g/L, the average crystal size (ACS) of ZnS QDs dropped from 5.95 to 3.34 nm, demonstrating the controlled biosynthesis of ZnS QDs. The ZnS QDs were coated or adhered to by both HPS and proteins, which played an important role in the controlled biosynthesis of ZnS QDs. The remarkable blue shift of the narrow UV absorption peak was due to the quantum confinement effect. The sequential variation in the colour of the photoluminescence spectrum (PL) from red to yellow suggested a tunable PL of the ZnS QDs. The current work demonstrated that SRB can fabricate the formation of ZnS QDs with a controlled size and tunable PL at a high-production rate of approximately 8.7 g/(L × week) through the simple mediation of HPS, with the yield being 7.46 times the highest yield in previously reported studies. The current work is of great importance to the commercialization of the biosynthesis of ZnS QDs.     

Luminescence enhancement of Mn doped ZnS nanocrystals passivated with zinc hydroxide

Mn-doped ZnS nanocrystals prepared by solvothermal method have been successfully coated with different thicknesses of Zn(OH)₂ shells through precipitation reaction. The impact of Zn(OH)₂ shells on luminescent properties of the ZnS:Mn nanocrystals was investigated. X-ray diffraction (XRD) measurements showed that the ZnS:Mn nanocrystals have cubic zinc blende structure. The morphology of nanocrystals is spherical shape measured by transmission electron microscopy (TEM). ZnS:Mn/Zn(OH)₂ core/shell nanocrystals exhibited much improved luminescent properties than those of unpassivated ZnS:Mn nanocrystals. The luminescence enhancement was observed with the Zn(OH)₂ shell thickening by photoluminescence (PL) spectra at room temperature and the luminescence lifetime of transition from ⁴T₁ to ⁶A₁ of Mn²⁺ ions was also prolonged. This result was led by the effective, robust passivation of ZnS surface states by the Zn(OH)₂ shells, which consequently suppressed nonradiative recombination transitions.     

硒化镉发光量子点的制备及其在有机发光器件中的应用

硒化镉量子点具有随粒径尺寸改变,而产生发光波长调变的特性,目前已被广泛研究。本研究是由化学溶胶法合成不同粒径尺寸的核壳型CdSe／ZnS硒化镉量子点,其表面包覆十六烷基胺,避免分子团聚现象。在由硒化镉成核温度的控制,成功地制备一系列具有各种尺寸粒径的核壳型硒化镉量子点(2—6nm)。本研究也合成了含有纳米金粒子于核壳型硒化镉量子点,实验结果发现：硒化镉发光效率明显的提高。在有机发光器件的应用方面,将发光波长为505nm核壳型CdSe／ZnS量子点掺入溶有发光波长为570nm铱化合物的氯仿溶液时,其溶液的光致发光光谱表明,原量子点的发光特性消失,只有铱化合物的发光依然存在,且其发光强度呈现明显增强趋势,我们推测此现象源自于量子点到铱化合物能量转移的机制。我们也以含有核壳型硒化镉量子点的铱化合物与PVK混合材料为发光层,成功的制作发光二极管器件,器件的发光效率因核壳型硒化镉的掺杂,明显提高2倍多。     

Surface modification and fluorescent properties of Mn2+-doped and undoped ZnS nanoparticles

Abstract

ZnS nanoparticles and Mn²⁺-doped ZnS nanoparticles were prepared by a reverse micelle reaction system. In addition, ZnS and Mn²⁺-doped ZnS nanoparticles were modified with poly(vinyl alcohol) (PVA) and 1-dodecanethiol (C₁₂H₂₅SH). The average particle size of the ZnS sample is determined around 2.3 nm by using the well-known Scherrer equation, which is in accordance with the results obtained from UV–vis and TEM analysis. Fluorescence intensity of the Mn²⁺-doped ZnS nanoparticles increases with increasing Mn²⁺ content compared with undoped ZnS nanoparticles, and coating PVA can also make fluorescence intensity increase. Different Zn²⁺/S^2- or C₁₂H₂₅SH/Zn²⁺ can affect intensity of PL emission peak and its position, which is discussed in this paper.     

热退火对ZnS:ErF3薄膜交流电致发光(ACEL)特性的影响

本文研究了退火温度以及退火时间的改变对ZnS:ErF3薄膜ACEL特性的影响。从ACEL光谱上可以看到,随退火温度增加或退火时间的积累,对应于4F9/2→4I15/2跃迁的谱线强度都有明显的增强。通过对EL衰减等实验结果进行分析,我们认为在不同的温度下退火将会产生不同的影响,当退火温度低于300℃时,退火将使ZnS的结晶性能得到改善,并使有效的发光中心数目增加,当退火温度高于300℃时,将产生一些新的缺陷。它们都导致了Er3+离子间交叉弛豫过程的加剧,使4F9/2能级的辐射得到加强。     

Synthesis and photoluminescent properties of ZnS:Cd nanoparticles and their phase-transferred nanocomposite with polyvinylpyrrolidone

ZnS:Cd nanoparticles were synthesized in a reverse micelle system by controlling reaction factors with mercaptoacetic acid (MPA) as a surfactant and N,N-dimethylformamide as an oil phase. X-ray diffraction pattern shows that the ZnS:Cd nanoparticles exhibit a cubic structure and its mean size is calculated around 4 nm. With different molar ratios of Zn²⁺/S^2?, the relative intensity of the emission peaks at 400 and 556 nm changes dramatically due to the more sulfur vacancies which resulted from the imbalance of Zn²⁺ and S²⁺ ions. Furthermore, hydrophobic phase-transferred ZnS:Cd nanoparticles were obtained using octylamine, and a highly luminescent phase-transferred ZnS:Cd/polyvinylpyrrolidone (PVP) nanocomposite was prepared by blending the phase-transferred ZnS:Cd with PVP. Infrared absorption suggests that octylamine has been successfully connected with the MPA-coated ZnS:Cd nanoparticles. Unlike the MPA-coated ZnS:Cd which has a very strong emission at 556 nm, the phase-transferred ZnS:Cd has a strong emission at 435 nm, which is ascribed to surface passivation and electron redistribution. In addition, luminescent intensity enhancement was observed for the phase-transferred ZnS:Cd/PVP nanocomposites with various Cd²⁺ doping concentrations.     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

金属铒和氟化铒掺杂的硫化锌薄膜的交流电致发光(ACEL)特性

本文报导了不同浓度的金属铒和氟化铒掺杂的硫化锌薄膜交流电致发光(ACEL)的特性,并进行了比较。实验结果表明:ZnS:ErF3薄膜ACEL的最佳浓度(5×10-3g/g)低于ZnS:Er3+薄膜ACEL的最佳浓度(1×10-2g/g)。在ZnS薄膜中掺入稀土离子,随着浓度的增加,稀土离子之间发生交叉弛豫,这一过程与稀土离子周围环境有关,这正是ZnS:ErF3和ZnS:Er3+薄膜ACEL具有不同的最佳浓度的主要原因。     

Photoluminescence of Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles applied in Bio-LED

In this work, transition elements, including Cu²⁺, Ag⁺, and Au³⁺, were used to dope in zinc sulfide (ZnS) by chemical solution synthesis to prepare Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles, respectively. Transition elements doping ZnS nanoparticles form the electronic energy level between the conduction band and valance band, which will result in the green light emission. There is a zinc sulfide emission shift from blue (~3.01 eV) to green light (~2.15 eV). We also found that Au:ZnS nanoparticles will emit a green light (~2.3 eV) and a blue light (~2.92 eV) at the same time because the mechanism of blue light emission was not broken after Au element had been doped. Furthermore, we used sodium chlorophyllin copper salt to simulate chlorophyll in biological light emission devices (Bio-LED). We combined copper chlorophyll with Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles by a self-assembly method. Then, we measured its photoluminescence spectroscopy and X-ray photoelectron spectroscopy to study its emission spectrum and bonding mode. We found that Au:ZnS nanoparticles are able to emit green and blue light to excite the red light emission of copper chlorophyll, which is a potential application of Bio-LED.     

Zinc sulfide nanoparticles: Spectral properties and photocatalytic activity in metals reduction reactions

Formation of zinc sulfide nanocrystals in aqueous solutions of various polymers has been studied. Spectral properties of ZnS nanoparticles have been investigated, the structure of the long-wave edge of the fundamental absorption band of ZnS nanocrystals has been analyzed. It has been shown that the variation of the synthesis conditions (stabilizer nature and concentration, solution viscosity, ZnS concentration, etc.) allows tailoring of the ZnS nanocrystals size in the range of 3–10 nm. Photochemical processes in colloidal ZnS solutions, containing zinc chloride and sodium sulfite, have been investigated. It has been found that the irradiation of such solutions results in the reduction of Zn(II), the rate of this reaction growing at a decrease in the size of ZnS nanoparticles. Kinetics of photocatalytic Zn(II) reduction has been studied. It has been concluded that two-electron reduction of adsorbed Zn(II) species is the rate-determining stage of this reaction. Photocatalytic activity of ZnS nanoparticles in KAu(CN)₂ reduction in aqueous solutions has been discovered. Spectral characteristics and kinetics of ZnS/Au⁰ nanocomposite formation have been studied. It has been shown that the photoreduction of gold(I) complex is the equilibrium reaction due to the reverse oxidation of gold nanoparticles by ZnS valence band holes.