纳米硫化锌的制备及光谱分析

采用超重力反应结晶法制备了纳米硫化锌粒子,并通过透射电子显微镜(TEM)、X射线粉末衍射仪(XRD)、X射线光电子能谱仪(XPS)、傅里叶红外光谱仪(FTIR)、紫外-可见光分光光度计(UV-Vis)和X射线能谱仪(EDX)对纳米硫化锌的形貌、结构、组成和光谱性能进行了细致分析。结果表明：超重力反应结晶法制备的纳米硫化锌粒子为球形,平均粒径为42 nm;XRD图谱表明纳米硫化锌呈现较好的闪锌矿晶型; XPS能谱表明纳米硫化锌的S(2p)的电子结合能为162.6 eV,Zn的2p_3/2,2p_1/2的电子结合能分别为1021.4, 1044.6eV。红外光谱研究表明纳米硫化锌在400～4 000cm-1范围内具有良好的红外透过率。紫外-可见光谱研究发现纳米硫化锌在200～340nm的紫外区域有较强的吸收,其禁带宽度为3.57eV。EDX能谱表明该法制备的纳米硫化锌具有较高的纯度。     

不同粒径纳米晶硫化锌的高压结构相变研究

 应用原位能量色散X射线散射和金刚石对顶砧技术，对纳米晶ZnS进行了高压结构相变研究。初始相为纤锌矿结构的10 nm和3 nm硫化锌分别在16.0 GPa和16.7 GPa时转变为岩盐矿结构，相变压力均高于纤锌矿结构的体材料硫化锌。该相变为一可逆的结构相变。应用大型科学计算软件Materials Studio（MS）计算了纳米晶ZnS的状态方程，根据Birch-Murnaghan方程拟合了纳米晶ZnS的零压体模量，得到的零压体模量高于相应体材料的零压体模量，表明纳米晶ZnS较难压缩。     

纳米硫化锌吸附剂中汞的稳定性研究

为了探究对纳米硫化锌吸附剂中汞的稳定性,采用重金属污染评价方法毒性特性浸出(TCLP)法对纳米硫化锌(Nano-ZnS)吸附的汞稳定性进行评价,并进一步研究了纳米硫化锌汞吸附量、浸提剂初始pH、浸出时间、液固比以及酸雨类型等对纳米硫化锌中汞稳定性的影响.结果表明:在偏酸性与偏碱性的条件下浸出液汞浓度较大,但是即使在pH=1与pH=13的情况下纳米硫化锌吸附的汞最大浸出浓度也仅分别为0.292μg/L与4.211μg/L。同时TCLP实验结果远低于TCLP标准中汞的安全浓度值25μg/L,说明纳米硫化锌吸附的汞具有良好的稳定性。     

纳米硫化锌吸附脱除单质汞的实验研究

在固定床吸附实验台上研究了N_2气氛下纳米硫化锌(Nano-ZnS)对单质汞的吸附脱除特性,分析了锌硫比(Zn:S)和干燥温度等制备条件以及反应床温度对其脱汞效果的影响,并和活性炭的脱汞性能进行对比。结果表明:锌硫比和干燥温度对吸附剂的脱汞性能影响很大,锌硫比为1:0.98,干燥温度为160℃时制备出的纳米硫化锌的脱汞性能最佳;纳米硫化锌对汞的吸附以化学吸附为主,在200℃左右,吸附作用最强;与商业活性炭相比,纳米硫化锌具有更优秀的汞吸附能力以及吸附速率。     

碲化镉纳米晶中温度相关的能量转移（英文）

为了获得纳米晶之间以及单个纳米晶内部本体态至缺陷态两种能量转移在不同温度下对发光强度的影响,测量了碲化镉纳米晶层发光光谱随温度(78~300K)的变化情况.碲化镉纳米晶层发光光谱显示:碲化镉纳米晶层在低温下有明显的本体(约520nm)和缺陷(约605nm)发光,且发光强度随温度的改变呈现出不同的变化规律.在温度变化的第一阶段(78~140K),大尺寸碲化镉纳米晶发光效率高、表面缺陷少,小尺寸纳米晶至大尺寸纳米晶间的能量转移使得纳米晶本体发光强度逐渐升高、缺陷发光强度迅速降低.在温度变化的第二阶段(140~300K),随着温度的升高,无辐射跃迁几率的增大使得碲化镉纳米晶缺陷态和本体态发光强度均逐渐降低.因此,能量转移仅在温度变化的第一阶段对发光强度的影响起主要作用,在第二阶段起次要作用.为了进一步验证能量转移对发光强度的影响,将碲化镉纳米晶用聚乙二醇包裹以减少纳米晶间的能量转移;将纳米晶层的干燥过程放在近真空环境下进行以减少单个纳米晶内部本体至缺陷态的能量转移.光谱结果显示在温度变化的第一阶段,这两种方式下得到的纳米晶层发光强度均逐渐降低,能量转移对发光强度的影响不再起主要作用.证实了能量转移对发光强度的影响规律的合理性.     

碲化镉纳米晶中温度相关的能量转移

为了获得纳米晶之间以及单个纳米晶内部本体态至缺陷态两种能量转移在不同温度下对发光强度的影响,测量了碲化镉纳米晶层发光光谱随温度(78～300 K)的变化情况.碲化镉纳米晶层发光光谱显示:碲化镉纳米晶层在低温下有明显的本体(约520 nm)和缺陷(约605 nm)发光,且发光强度随温度的改变呈现出不同的变化规律.在温度变化的第一阶段(78～140 K),大尺寸碲化镉纳米晶发光效率高、表面缺陷少,小尺寸纳米晶至大尺寸纳米晶间的能量转移使得纳米晶本体发光强度逐渐升高、缺陷发光强度迅速降低.在温度变化的第二阶段(140～300 K),随着温度的升高,无辐射跃迁几率的增大使得碲化镉纳米晶缺陷态和本体态发光强度均逐渐降低.因此,能量转移仅在温度变化的第一阶段对发光强度的影响起主要作用,在第二阶段起次要作用.为了进一步验证能量转移对发光强度的影响,将碲化镉纳米晶用聚乙二醇包裹以减少纳米晶间的能量转移;将纳米晶层的干燥过程放在近真空环境下进行以减少单个纳米晶内部本体至缺陷态的能量转移.光谱结果显示在温度变化的第一阶段,这两种方式下得到的纳米晶层发光强度均逐渐降低,能量转移对发光强度的影响不再起主要作用.证实了能量转移对发光强度的影响规律的合理性.     

六方相纤锌矿硫化锌微球的制备及性能研究

以谷胱甘肽(GSH)为硫源,氯化锌(ZnCl2)为锌源,溴化十六烷基三甲铵(CTAB)为表面活性剂,乙二胺为反应媒介,采用水热法在较低温度(160℃)下成功地合成六方相纤锌矿硫化锌(ZnS)纳米微球。采用扫描电子显微镜观察纳米微球的形貌,利用X射线衍射仪分析其物相,借助荧光光谱仪和紫外分光光度计分析不同条件下合成的硫化锌纳米微球的光学性能。实验结果表明,CTAB能够促进空心微球的形成,以CTAB为致孔剂能够在相对较低的温度条件下得到由纳米粒子组成的微米量级的单分散六方相纤锌矿结构的硫化锌微球。通过改变其他反应参数可以得到不同壳厚的硫化锌微球,测试其发光性能发现空心球的荧光效果明显好于实心球。     

SmCo7纳米晶合金晶粒组织热稳定性的热力学分析与计算机模拟

推导出了单相纳米晶合金的晶界过剩体积与晶粒尺寸之间的定量关系, 建立了纳米晶合金的晶界热力学性质随温度和晶粒尺寸发生变化的确定性函数. 针对SmCo₇纳米晶合金, 通过纳米晶界热力学函数计算和分析, 研究了单相纳米晶合金的晶粒组织热稳定性. 研究表明, 当纳米晶合金的晶粒尺寸小于对应于体系中晶界自由能最大值的临界晶粒尺寸时, 纳米晶组织处于相对稳定的热力学状态; 当纳米晶粒尺寸达到和超过临界尺寸时, 纳米晶组织将发生热力学失稳, 导致不连续的快速晶粒长大. 利用纳米晶合金热力学理论与元胞自动机算法相耦合的模型对SmCo₇纳米晶合金在升温过程中的晶粒长大行为进行了计算机模拟, 模拟结果与纳米晶合金热力学模型的计算预测结果一致, 由此证实了关于纳米晶合金晶粒组织热稳定性的研究结论. 关键词： 纳米晶合金热力学 7纳米晶合金')" href="#">SmCo₇纳米晶合金 热稳定性 计算机模拟     

形状和原子数对纳米晶表面能的影响

确定了德拜温度与原子相互作用势的相互关系以及直角形纳米晶原子的平均配位数与形状和 原子数的关系.应用统计物理理论得到直角形纳米晶的表面能随温度、原子数和形状的变化 规律.以Ar纳米晶为例，讨论了形状和原子数对纳米晶表面能的影响. 关键词： 纳米晶 表面能 形状和线度     

非荧光硫化锌纳米簇的合成与表征

合成硫化锌纳米簇并对其进行表征, 建立一种利用硫化锌纳米簇的阳离子交换(CX)反应检测痕量生物分子的方法。采用水热法合成非荧光硫化锌纳米簇(NCCs)并对其进行表征。纳米簇的性能直接影响检测结果。通过透射电镜图像和X射线衍射可知, 纳米簇是多孔的, 可以通过快速阳离子交换反应从纳米簇中释放大量的Zn2+, 在锌响应试剂的作用下产生荧光信号进行荧光检测。其晶体的外部比内部排列松散, 有利于快速阳离子交换, 其晶体尺寸大小与加热时间有关。通过比表面积检测法测定纳米簇的表面积和孔径表明, 最小的纳米簇拥有相对较大的表面积及较高的阳离子交换效率。实验了三种释放方法(酸溶解法、阳离子交换法和微波辅助阳离子交换法)对Zn2+释放性能的影响, 结果表明, 微波辅助阳离子交换法信噪比较高, 操作简便, 可用于硫化锌纳米簇免疫测定法中。比较了Zn2+的释放效率和目标结合力与平均直径之间的关系, 结果表明纳米簇尺寸为44 nm时表现出最高的阳离子交换效率。结论: 所有这些特点, 使ZnS纳米簇阳离子交换放大器在痕量生物分子检测方面成为高度灵敏、生物相容性好、低廉环保的检测工具。     

玻璃中的ZnS:Mn2+超微粒发光的量子尺寸效应

自从Bhargava等^[1]报道了化学反应合成的ZnS:Mn²⁺纳米微粒的光学性质,掺杂半导体纳米微粒发光性质的研究受到了极大的重视。掺杂纳米微粒有可能成为新的一类发光材料.本文报导用熔融法制备的ZnS:Mn²⁺玻璃在光学性质上的量子尺寸效应。     

Structural and optical properties of monodispersed ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles

Excellent luminescence properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanocrystallites synthesized through a simple chemical method at room temperature are reported. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV–visible absorption and photoluminescence techniques were used to characterize the undoped ZnS, CdS and ZnO and the novel ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles. The optical properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles reflect a combinational effect of the photoluminescent properties of ZnS, CdS and ZnO.     

ZnS型发光材料光老化的研究

用X射线衍射谱证实了ZnS光致发光材料经紫外线照射后,体色逐渐变灰至黑是由于ZnS离解析出Zn所引起并发现尚有其它组分存在.还研究了不同波长的紫外线照射和材料粒经大小对ZnS发光材料光老化的影响得出一些新的实验结果.     

Electro- and photoluminescence of compounds based on doped zinc sulfide in the 500–750-nm range

The influence of atmospheric passivation on the electro- and photoluminescent properties of ZnS powders doped with In and/or CuCl is investigated. The processes proceeding in the material during thermal doping with In and/or CuCl as well as participation of oxygen in forming the electro- and photoluminescent radiation centers are discussed. The possibility of creating electro- and photoluminophors based on ZnS that have a continuous spectrum in the visible range with the same spectral density is shown. An electroluminophor based on ZnS:In,Cu,Cl that emits radiation with practically the same spectral density in the 550–750-nm range has been created as well as a photoluminophor based on ZnS:In that emits similarly within the range 500 < < 700 nm.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 90–93, January–February, 2005.     

Photoluminescent properties of ZnS nanoparticles prepared by electro-explosion of Zn wires

We study the photoluminescent properties of ZnS nanoparticles without the influence of dopants or magnetic impurities. The ZnS nanoparticles reported in this case were synthesized by a novel method of electro-explosion of wire (EEW). The nanoparticles were prepared employing electro-explosion of pure zinc wires in a cell filled with sulfide ions to produce a free-standing compound ZnS semiconductor. To investigate the structural and optical properties, these nanoparticles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), UV–visible and photoluminescence (PL) spectroscopy. Consistent with the enhancement of the PL intensity of the 443 nm peak due to deep blue emission of ZnS particles, the XRD of the nanoparticles reveals a hexagonal phase of ZnS nanocrystallites prepared by our novel synthesis technique.      

Synthesis and characterisation: Zinc oxide–sulfide nanocomposites

A novel synthesis method is presented for the preparation of nanosized-semiconductor zinc oxide–sulphide (ZnO/ZnS) core–shell nanocomposites, both formed sequentially from a single-source solid precursor. ZnO nanocrystals were synthesized by a simple co-precipitation method and ZnO/ZnS core–shell nanocomposites were successfully fabricated by sulfidation of ZnO nanocrystals via a facile chemical synthesis at room temperature. The as-obtained samples were characterized by X-ray diffraction and transmission electron microscopy. The results showed that the pure ZnO nanocrystals were hexagonal wurtzite crystal structures and the ZnS nanoparticles were sphalerite structure with the size of about 10 nm grown on the surface of the ZnO nanocrystals. Optical properties measured reveal that ZnO/ZnS core–shell nanocomposites have integrated the photoluminescent effect of ZnO and ZnS. Based on the results of the experiments, a possible formation mechanism of ZnO/ZnS core–shell nanocomposites was also suggested. This treatment is suggested to improve various properties of optoelectronically valuable ZnO/ZnS nanocomposites. These nanosized semiconductor nanocomposites can form a new class of luminescent materials for various applications.     

Study of energy transfer from capping agents to intrinsic vacancies/defects in passivated ZnS nanoparticles

The study of energy transfer mechanism from different capping agents to intrinsic luminescent vacancy centres of zinc sulphide (ZnS) has been reported in the present work. Nanoparticles of capped and uncapped ZnS are prepared by co-precipitation reaction. These nanoparticles are sterically stabilized using organic polymers—poly vinyl pyrrolidone, 2-mercaptoethanol and thioglycerol. Monodispersed nanoparticles were observed under TEM for both capped and uncapped ZnS nanopowders. However, for uncapped ZnS nanopowders, tendency for formation of nanorod like structure exists. Size of ZnS crystallites was calculated from X-ray diffraction pattern. The primary crystallite size estimated from X-ray diffraction pattern is 1.95–2.20 nm for capped nanostructures and 2.2 nm for uncapped nanostructures. FTIR spectra were conducted to confirm capping. Zeta potential measurements have been done to check the stability of dispersed nanoparticles. Band gap measurement was done by UV–visible spectrophotometer. Excitation and emission spectra are also performed in order to compare optical properties in various samples. Increase in emission intensity and band gap has been observed by adding different capping agents in comparison to uncapped ZnS nanoparticles. The results show that in capped ZnS nanoparticles the mechanism of energy transfer from capping layer to photoluminescent vacancy centres is more pronounced.     

The Dynamic Resistance of CdS/CdSe/ZnS Co-Sensitized TiO2 Solar Cells

Quantum dots' sensitized solar cells (QDSSCs) can create the high-performance and low-cost photovoltaic in the future. In this study, we synthesized the film of TiO₂/CdS/CdSe/ZnS photoanodes by successive ionic layer adsorption reaction (SILAR) method. The absorption spectra, photoluminescent spectra and electrochemical impedance spectra (EIS) of the film TiO₂/CdS/CdSe/ZnS photoanodes show that the structure of energy levels in the conduction band (CB) of photoanode materials CdS, CdSe, and ZnS quantum dots (QDs) can absorb a great number of photons in each region and inject stimulated electrons quickly into the conduction band (CB) of TiO₂. Furthermore, we also studied the influence of the SILAR cycles on the dynamic resistance, the lifetime of electrons in QDSSCs through Nyquist and Bode.     

Mercaptopropionic acid capped CdSe/ZnS quantum dots as fluorescence probe for lead(II)

MPA stabilized CdSe/ZnS NCs was applied as a fluorescent probe for the sensitive detection of Pb²⁺ in water. The microreaction was demonstrated as a facile method for the reproducible synthesis of CdSe/ZnS NCs with a high quantum yield. The good stability of CdSe/ZnS NCs was proved by the significant maintaining of photoluminescent (PL) after the ligand exchange with MPA, and was further demonstrated by the excellent PL property in water solution with various pH values. The cation exchange of Zn with Pb led to the linear quenching of PL with the concentration of Pb²⁺, which provided as an opportunity to apply MPA stabilized CdSe/ZnS NCs as fluorescent probes for Pb²⁺. A facile method by adjustment of QDs concentration was demonstrated as a suitable way to approach different detection limits. The detection limits of 0.03 and 3.3 μM were achieved by setting QDs solutions with the absorbance of the first exciton peak as 0.05 and 0.15, respectively.     

Synthesis and characterization of ZnS:Cu,Al phosphor prepared by a chemical solution method

A novel and simple synthesis route for the production of ZnS:Cu,Al sub-micron phosphor powder is reported. Both the host and activator cations were co-precipitated from an ethanol medium by mixing with a diluted ammonium sulfide solution. The co-precipitated ZnS:Cu,Al was in cubic zinc blende structure after an intermediate-temperature furnace annealing. Strong photoluminescent and cathodoluminescent (CL) emission were observed, which was attributed to the 3d¹⁰-3d⁹4s¹ radiative transition at those copper sites. At an accelerating voltage of 1 kV, the CL intensity of the co-precipitated ZnS:Cu,Al sample was recorded 94% of the commercial reference phosphor with the same composition made by high temperature solid-state-reaction method. The particle size of the co-precipitated phosphor powders was found to be controllable simply through adjusting the reactant concentrations. The particle size of the annealed samples was measured by dynamic light scattering, which showed a mean particle diameter between 200 and 700 nm depending on the co-precipitation conditions.