硫化锌纳米晶的合成及性能表征

采用水热法以油酸和十二烷基硫酸钠(简记为SDS)作为复合型表面活性剂制备ZnS纳米晶,并对制备的ZnS纳米晶进行了表征.通过正交实验考察了油酸用量、SDS用量、反应温度、反应时间及pH值对ZnS发光性能的影响,确定了最佳工艺条件.结果表明,制备的ZnS为闪锌矿结构,单分散,粒径尺寸为6 nm,ZnS纳米晶表面的亲水性得到了有效的改善.所以,复合型表面活性剂的使用既可以提高ZnS纳米晶的发光性能又起到表面改性的作用.     

声化学法合成ZnS纳米晶及反应动力学研究

采用声化学法制备了ZnS纳米晶,对其反应动力学进行了研究,利用XRD、TEM等手段对样品进行了表征.结果表明,以无水氯化锌、硫代乙酰胺为原料,采用声化学法可以制备粒径在10 nm左右的ZnS纳米晶,所得样品为α-ZnS纤锌矿结构,六方晶系,形貌为球形或近球形.随超声功率增加,ZnS纳米晶粒度降低.动力学研究表明,ZnS纳米晶的生成量随时间呈线性增加,ZnS纳米晶的生成活化能为29.88 kJ/mol.     

功能化ZnS:Mn/ZnS纳米微粒的制备及光学性质的研究

本文采用反相微乳液法制备了核壳结构的ZnS:Mn/ZnS纳米微粒.为了获得具有一定水溶性及生物相容性的纳米颗粒,巯基乙酸被直接加入到反相微乳液体系中对ZnS:Mn/ZnS纳米颗粒进行表面改性.连接上巯基乙酸的ZnS:Mn/ZnS纳米微粒在600nm处的光致发光明显增强.实验结果显示导致荧光增强的机理可能是有机分子及多核锌配合物的钝化作用.     

Ag/ZnS核壳结构纳米棒的制备及其光催化性能分析

在制备的Ag纳米线的基础上,用水热法合成了Ag/ZnS核壳结构纳米棒.使用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、X射线能谱仪(EDS)、高分辨透射电子显微镜(HRTEM)、紫外-可见双光束分光光度计(UV-vis)、光致发光扫描仪(PL)等检测设备对样品的成分、形貌、微结构及光学性能进行了表征.结果显示,制备的Ag/ZnS复合材料为ZnS纳米颗粒包覆Ag纳米线的核壳结构,其紫外吸收峰位于350 nm处,相对于ZnS纳米颗粒变宽并发生红移,PL发射峰位于462 nm处,相对于ZnS纳米颗粒发生了蓝移,强度明显降低.光催化结果显示,Ag/ZnS核壳结构纳米棒的光催化性能优于ZnS纳米颗粒,分析了光催化反应机理.     

ZnS:Mn/CdS核壳结构纳米微粒的制备及光学特性

采用微乳液法制备了掺Mn的ZnS纳米微粒并用CdS对其进行了表面修饰,以XRD、紫外吸收和发射光谱对其结构及光学性质进行了表征和研究.制得的纳米微晶粒径为4～6nm,为立方纤锌矿结构.与未经包覆的ZnS:Mn纳米微粒相比,核壳结构的ZnS:Mn/CdS纳米微粒中Mn2+发射峰的强度增强了很多,适当厚度的壳层的修饰可减少其表面态发射和非辐射跃迁,增强了Mn2+离子的4T1-6A1的能量传递和ZnS的带边发射,提高了发光效率;讨论了ZnS核中Mn掺杂浓度对ZnS:Mn/CdS纳米微晶的光学性能的影响,发现当掺Mn浓度为4;时Mn2+发射峰的强度最大.     

脉冲电沉积结合水热法制备ZnS纳米条及其光学性质的研究

用水热法在脉冲电沉积纳米ZnS晶种的衬底上,制备了ZnS纳米条.利用XRD、SEM、EDS对ZnS的形貌和结构进行了表征,通过UV、PL研究了ZnS的光学性质.结果表明,ZnS晶种的存在、形貌控制剂(5-磺基水杨酸)的添加对ZnS显微形貌和光学性质有重大影响.重点讨论了形貌控制剂的添加顺序对ZnS形貌的影响.产物ZnS为闪锌矿结构,发蓝光,组成均匀,对紫外光的透过率较低,光学禁带宽度变宽.     

ZnS-CdS核壳纳米微晶的制备与光学特性

采用微乳液法制备了核壳结构ZnS/CdS纳米微晶.以XRD、TEM表征其结构、粒度和形貌,UV、PL表征其光学性能.制得的纳米微晶近似呈球形,粒径4～5nm.研究了不同CdS壳层厚度的ZnS/CdS纳米微晶的光学性能,PL谱表明壳层CdS的修饰可减少ZnS的表面缺陷,表面态发射和非辐射跃迁减少,带边直接复合发光的几率增大,发光效率大大提高;在壳层CdS达到一定厚度时,PL谱却表现为CdS的特征发射,同时发现核心ZnS对壳层CdS的发光具有增强作用,提出了ZnS/CdS发光机理的能带模型.     

反相微乳液法制备CdS/ZnS纳米晶及其表征

用反相微乳液法制备了CdS纳米粒子,以ZnS对其表面进行包裹,得到了核壳结构的CdS/ZnS纳米晶.采用X射线衍射(XRD)、透射电镜(TEM)表征其结构、粒度和形貌,紫外-可见吸收光谱(UV-VIS)、光致发光光谱(PL)表征其光学特性.制得的CdS纳米微粒近似呈球形,直径约3.6nm;包裹以后颗粒仍为球形,粒径约10nm,以XRD、UV-VIS和PL证实了CdS/ZnS核壳结构的实现.文章还研究了不同Zn/Cd的摩尔比对CdS/ZnS纳米微粒光学性能的影响,UV-VIS谱表明随着壳层厚度的增加CdS/ZnS纳米晶的吸收带边有轻微的红移;PL谱表明壳层ZnS的包覆可减少CdS纳米微粒的表面缺陷,带边直接复合发光几率增大,且具有合适的壳层厚度时,CdS核层的发光效率有较大提高.     

功能化ZnS∶Mn/ZnS纳米微粒的制备及光学性质的研究

本文采用反相微乳液法制备了核壳结构的ZnS∶Mn/ZnS纳米微粒。为了获得具有一定水溶性及生物相容性的纳米颗粒,巯基乙酸被直接加入到反相微乳液体系中对ZnS∶Mn/ZnS纳米颗粒进行表面改性。连接上巯基乙酸的ZnS∶Mn/ZnS纳米微粒在600nm处的光致发光明显增强。实验结果显示导致荧光增强的机理可能是有机分子及多核锌配合物的钝化作用。     

声化学法制备ZnS: Mn纳米晶及其光学性能

以无水氯化锌,四水氯化锰以及硫代乙酰胺为原料,采用声化学法成功制备了锰掺杂的ZnS(ZnS: Mn)纳米晶.采用透射电子显微镜镜(TEM)、X射线能谱仪(EDS)、X射线粉末衍射(XRD)和光致发光谱(PL)对所制得的纳米进行了表征.结果表明:所制备ZnS: Mn为立方闪锌矿结构,纳米粒子的形貌接近于球形.平均晶粒尺寸为10 nm左右.PL光谱分析表明:所制备试样有两个主要的发射峰,分别位于在480 nm和570 nm左右,后者与体材料ZnS: Mn相比发生了明显蓝移,但仍表现为橙黄色发光.Mn2+掺杂浓度对ZnS: Mn的光致发光性能有显著影响,原料中Zn: Mn: S(物质的量比)为3: 1: 4,Mn2+掺杂浓度为2.64 at;时,光致发光光谱发射峰强度达到最大值.     

Homoepitaxial growth and photoluminescence of self‐assembled In‐doped ZnS nanowire bundles

Self‐assembled In (Indium)‐doped ZnS nanowire bundles were synthesized via a thermal evaporation method without using any template. Vapor ‐ solid homoepitaxial growth was found to be the key reason for the formation of close‐packed nanowire bundles grown on the surface of microscale sphere‐shaped ZnS crystal. X‐ray diffraction (XRD), selected area electron diffraction (SAED), and transmission electron microscopy (TEM) analysis demonstrate that the In‐doped ZnS nanowires have the cubic structure, and there are numerous stacking faults along the <111> direction. Photoluminescence (PL) spectrum shows that the spectrum mainly includes two parts: a weak violet emission band centering at about 380 nm and a strong green emission band centering at about 510 nm. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave hydrothermal synthesis and photocatalytic properties of ZnWO4 nanorods

Cd²⁺‐doped ZnWO₄ nanorods have been synthesized at 200 °C with microwave hydrothermal method, using Zn(NO₃)₂·6H₂O, Na₂WO₄·2H₂O and CdCl₂ as raw materials. The effects of Cd²⁺ doping contents on the structure and morphology of the product were studied. The results show that Cd²⁺ doping into the crystal lattice of ZnWO₄ nanopowder makes the powder orientationally grow along (010), (110) and (200) crystal planes to form the nanorods. The bigger Cd²⁺ doping contents are, the more obviously ZnWO₄ nanorods grow. Meanwhile, the nanopowder is gradually transformed from monoclinic phase into the orthogonal phase. As the charge transference medium between the interfaces, Cd²⁺ restrains the combination of holes and electrons. After doped, the photocatalytic properties of ZnWO₄ nanorods are increased. When Cd²⁺ doping content is 20%, the Cd²⁺‐doped ZnWO₄ nanorods showed the highest degradation rate up to 98% in 2 h.     

Luminescence characteristics of undoped and Eu‐doped GdCa4O(BO3)3 single crystals and nanopowders

Single crystals of GdCa₄O(BO₃)₃ (GdCOB) pure and doped with Eu concentration of 1 and 4 at% were grown by the Czochralski and micropulling‐down methods. The distribution of Eu ions in GdCOB crystals was uniform. The substitutions of Eu³⁺ in Gd, Ca(1) and Ca(2) cation sites and eventually formation Eu²⁺ have been investigated. The spectroscopic properties of crystals are compared with the properties of nanopowders obtained by sol‐gel method. Radioluminescence spectra of undoped GdCOB crystal show the characteristic emission of Gd³⁺ at about 312 nm, whereas this emission dramatically decreases in Eu‐doped crystals upon X‐ray excitation, as well as in Eu‐doped nanopowders excited in vacuum ultraviolet (VUV) region. The VUV excitation in the range 125‐333 nm for Eu‐doped samples leads to strong emission in red coming from the ⁵D₀ multiplet of Eu³⁺, only. In the photoluminescence decay kinetics of 312 nm emissions substantial shortening and departure for single exponential decay in Eu‐doped samples is clearly observed. Higher Eu doping results in further acceleration of the decay. In undoped GdCOB crystal, the lifetime of the Gd^{3+ 6}P_7/2 multiplet is 2.79 ms. The Eu^{3+ 5}D₀ decay kinetics monitored at 613 nm are rather constant. Numerical fitting of fully exponential curves, reveals lifetimes 2.7 ms for nanopowder and 2.5 ms for single crystal. The results suggest that this material may be used as a red phosphor in plasma display panels in nanopowder form because of strong excitation band of Eu³⁺ luminescence in the 160‐200 nm regions. Contrary to nanopowder sample, such an excitation band, attributed to the Gd³⁺–O^2– charge transfer was not observed in crystal obtained by the micropulling‐down method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth,spectral and thermal properties of KAP single crystals in the presence of DL‐Alanine and L‐Methionine amino acid dopants

Single crystals of potassium acid phthalate (KAP) and amino acid (DL‐Alanine, L‐Methionine) doped KAP were grown from aqueous solutions by slow cooling method. The grown crystals were characterized using powder X Ray diffraction (XRD) and Fourier Transform Infrared (FTIR) analysis. The thermal stability of KAP in the presence of dopants was analysed using Thermogravimetric and Differential Scanning caloriemetric (TGA/ DSC) studies and the maximum temperature for non linear optical application of this compound in the presence of dopants was found out. The transmittance of KAP was found to increase in the presence of dopants. Etch pits were observed for all the crystals using different etchants. Vickers microhardness tests were performed to study the mechanical stability of the crystals. The hardness of DL‐alanine doped KAP is more than that of L‐alanine doped KAP crystal. The dielectric constant and loss were determined as a function of temperature. Frequency response of the dielectric constant and dielectric loss factor have been studied over the frequency range of 50Hz – 5MHz. Second harmonic generation (SHG) was confirmed in all the crystals using the Kurtz and Perry powder technique. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Conversion from ZnO nanospindles into ZnO/ZnS core/shell composites and ZnS microspindles

The formation process of ZnO/ZnS core/shell microcomposites and ZnS microspindles prepared by the reaction of ZnO colloids and thioacetamide under hydrothermal conditions was investigated in detail by X‐ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy and selected‐area electron diffraction techniques. The precursors of spindlelike ZnO colloids were prepared by a hydrothermal method with the help of a surfactant. A growth mechanism was proposed to account for the formation of ZnO/ZnS core/shell microcomposites and ZnS microspindles. Luminescence measurement revealed that ZnO/ZnS core/shell microcomposites integrated the luminescence effect of ZnO and ZnS. The blue and green emissions were dramatically enhanced, while the orange emission disappeared. The results provide a good approach to tune the visible emission of the ZnO nanostructures by ZnS coating. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

掺三氟乙酸TGS晶体生长及其性能研究

本文以三氟乙酸作为掺质,分别按4.4mol%、9.4mol%、13.4mol%、18.4mol%的配比进行了掺质TGS晶体生长,并对其作X射线粉末衍射分析及晶体热释电性能的测试。结果表明,三氟乙酸的掺入虽然使热释电性能有一定程度下降,但却使得晶体铁电-顺电相转变延迟,提高了晶体的居里点,并产生了一定的内偏压场。     

掺杂TGS晶体的生长及热释电性能研究

选择重稀土离子Dy3 为掺杂阳离子,DL-丙氨酸与L-谷氨酸部分取代甘氨酸分子,生长了不同掺杂配比的TGS晶体。生长和测试实验表明,掺杂TGS晶体较纯TGS晶体易于生长。将掺杂晶体生长溶液的pH值控制在1~4,可改变掺杂晶体的结晶习性。用ICP发射光谱测试了掺杂晶体中稀土元素的含量,用X射线粉末衍射法测定了晶格参数,结果表明:元素已进入晶体,晶格参数稍有变化,但掺杂晶体的对称性仍为C2-2。通过测量掺杂晶体的电滞回线,得到了内偏压场,还测量了各样品的热释电系数、自发极化强度,作了温度曲线,并分析了各掺杂剂对提高热释电性能和锁定极化的作用。结果表明:是有应用前景的热释电材料。     

Dielectric and microhardness studies on L‐citrulline and L‐ascorbic acid admixture TGS crystals

Single crystals of amino acid doped (L–citrulline, L‐ascorbic acid) triglycine sulphate were grown by slow evaporation technique. The lattice parameters and crystalline quality were confirmed by powder X‐ray diffraction studies. The presence of functional groups in the grown crystals was confirmed by Fourier transform infrared spectrum analysis. The dielectric studies were carried out to identify the phase transition temperature and the dielectric constant was found to be less for both the doped crystals than pure triglycine sulphate crystal. Micro hardness studies were carried out using Vickers pyramidal indentation technique at room temperature showed a decrease in hardness due to doping. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vapour-phase epitaxial growth of ZnS on GaP

Single crystal layers of ZnS about 100 μm thick were grown epitaxially on GaP substrates in an open tube system using source ZnS powder and a flowing hydrogen atmosphere. The growth rate for different substrate temperatures increases with increasing hydrogen flow rate, but the growth rate profiles resemble each other in shape. The profile shifts towards the low temperature side as the source temperature is decreased. The (111)B substrate orientation is found to be preferable to the (111)A or the (100) with respect to surface morphology and crystal quality. X-ray diffraction investigations and luminescent properties show that the (111)B grown layers are of high quality. All ZnS layers grown on GaP substrates are craked on cooling, which may be due to the thermal expansion mismatch between the layer and the substrate. Heat-treatment of the grown layer does not reduce the resistivity, but increases the photoluminescence intensity markedly. Selective vapour-phase epitaxial growth has been successfully applied resulting in crack-free ZnS layers on GaP substrates.     

Growth and characterization of doped hippuric acid crystals for NLO devices

Modified hippuric acid (HA) single crystals have been grown from aqueous solution of acetone by doping with NaCl and KCl using slow evaporation technique at constant temperature, with the vision to improve the physicochemical properties of the sample. The characterisation of grown crystals was made by X‐ray powder diffraction, density and melting point measurements. TGA/DTA studies indicate that doped crystals are more stable than pure crystals. The optical transmission study and Kurtz powder SHG measurement shows the suitability of doped crystals for NLO applications. Dopant concentration is identified with ICP atomic emission spectrometer system. The Vicker's hardness studies at room temperature, carried out on (111) crystallographic plane shows increased hardness of the doped crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)