Mn~(2+)掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,在3-巯基丙酸(MPA)为表面修饰剂下,成功制备出Mn2+掺杂水溶性ZnS量子点。利用X射线衍射仪、透射电子显微镜、紫外-可见吸收光谱仪和荧光分光光度计等表征方法研究了Mn2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明,所得产物为ZnS立方型闪锌矿结构,样品呈不规则球形,粒径主要集中在9.7nm左右;在320nm激发下,Mn2+掺杂ZnS量子点出现两个发射波峰,分别位于587和637nm处,其中587nm处的发射波峰为ZnS表面态缺陷发光,而637nm处的发射波峰则属于Mn2+∶4T1-6A1能级特征发光。同时,利用红外吸收光谱对Mn2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

低温水热法制备ZnS:Co+Cr纳米晶及其光学性能研究

采用低温水热法制备出3-巯基丙酸(MPA)修饰的ZnS:Co+Cr纳米晶. 利用X射线衍射仪、粒度分析仪、透射电镜、紫外-可见分光光度计、荧光分光光度计和XPS能谱仪等对ZnS:Co+Cr纳米晶的结构、形貌、粒径分布和发光性能进行了表征. 结果表明: 合成的ZnS:Co+Cr纳米晶有较好的单分散性, 平均粒径为9.3 nm, 均为立方闪锌矿结构; ZnS:Co+Cr纳米晶的吸收边位于320 nm处, 并在728 nm处出现Co²⁺的特征吸收峰; 当Cr²⁺浓度为0.75at%, 水热反应温度为160℃时, ZnS:Co+Cr纳米晶PL峰最强; XPS能谱表明Cr²⁺部分被氧化成Cr³⁺。     

水溶性ZnS量子点的共沉淀法制备、 表征及其光学性能

以硫化钠和乙酸锌为反应物,3-巯基丙酸为表面包覆剂,利用共沉淀法制备了水溶性ZnS量子点。并采用X射线衍射仪、透射电子显微镜和荧光分光光度计等对样品的结构、形貌、粒径和光学性能进行了表征。结果表明:所得样品为ZnS立方型闪锌矿结构,量子点的形状呈不规则球形,粒径主要集中在4.8nm左右;样品在585～590nm之间出现了黄色荧光发射波峰。同时,利用红外光谱对ZnS量子点的合成机理进行了初步分析。     

Ⅱ-Ⅵ族量子点掺杂玻璃的光学性质及研究进展

由于量子限域效应,尺寸可调的Ⅱ-Ⅵ族量子点掺杂玻璃在光学滤波片、非线性光学器件上的应用已经被广泛研究。玻璃中量子点的光学性质主要由量子点的尺寸、表面状态和周围基质环境决定,通过提高Se/Cd比可以有效地对量子点的表面缺陷进行钝化,实现CdSe量子点的本征发光;进一步调整热处理制度可以促进Zn离子扩散进入CdSe量子点表面,形成CdSe/Cd_(1-x)Zn_xSe核壳结构,使得缺陷发光几乎完全猝灭,从而提高量子点的荧光量子效率;在玻璃中原位合成的CdS/ZnS核壳结构量子点的荧光量子效率可达到53%。随着基础研究中玻璃中Ⅱ-Ⅵ族量子点荧光效率的不断提高,发光二极管(LED)等小型发光器件的制造成为可能。为了满足实际需要,建立核壳结构中量子点表面钝化机理模型,进一步优化量子点荧光效率是下一步需要解决的问题。     

CdSe与CdSe/ZnS量子点合成及稀土掺杂

在LSS(liquid-solid-solution)多相体系中制得了CdSe、CdSe/ZnS量子点和Eu掺杂的量子点。利用TEM、XRD、PL、EDS对产物进行了表征。TEM结果显示所得的量子点形貌规则、尺寸均匀。XRD结果显示CdSe/ZnS量子点呈六方晶系。PL结果对比表明,合适厚度壳层ZnS包覆后的CdSe量子点发光效率明显提高,发光峰的半高宽有大幅度提高,并分析了所得的结果。掺杂稀土元素Eu后,CdSe(Eu)量子点在红光区域产生了新的发光峰;而CdSe(Eu)/ZnS量子点在红光区域内没有出现发光峰,并阐明了这种现象的原因。     

圆偏振光诱导CdTe量子点再生长及其对光致发光的影响

实验研究了以3-巯基丙酸为配体合成的水溶性CdTe量子点经过非偏振光与圆偏振光照射处理后, 量子点的再生长变化规律。采用光致发光谱、紫外-可见吸收光谱、透射电子显微镜与X射线衍射等表征手段分析表明: 非偏振光会促进CdTe量子点的光氧化, 导致量子点尺寸缩小, 荧光发光峰位蓝移, 且发光效率降低; 而圆偏振光增强了配体的光氧化, 在量子点表面形成CdS层, 导致量子点尺寸进一步增大, 荧光发光峰红移, 且发光效率提升。进一步讨论了CdTe量子点与配体之间的键合作用, 相关光化学反应机制及其对量子点光致发光性质的影响。     

CuInS2/ZnS核壳结构量子点的水相制备与性能研究

因不含Cd、Pb、Te等有毒元素, 且具有在可见光至近红外光波段可调的发光性能, 铜铟硫(CuInS₂)量子点作为一种新型的I-III-VI型三元半导体材料, 广泛应用于分析检测和生物成像等领域。本研究采用一种低毒低温的方法快速合成CuInS₂量子点及其ZnS核壳结构量子点, 不仅利用ZnS带隙较宽且表面缺陷少的特点, 弥补了CuInS₂量子点的劣势, 提高了CuInS₂量子点的发光性能; 同时由于低毒性ZnS壳层的包覆, 进一步降低生物毒性。当Cu∶In摩尔比为1∶1时, CuInS₂量子点于530 nm处出现明显的发射峰, 且随着In含量的增加, 发光峰逐渐红移。包覆ZnS壳层后, CuInS₂量子点的发光强度明显增大, 且谱峰明显红移。当Cu∶Zn比为1∶1, 回流时间为45 min时, 合成的CuInS₂/ZnS量子点发光性能最优。该合成方法节省能源、生产效率高、绿色环保, 具有较大的应用前景。     

N-B-Al共掺荧光4H-SiC施主受主对发光性能研究

施主受主共掺杂的荧光4H-SiC可以通过复合发出可见光, 影响其发光性能的一个重要因素是施主-受主掺杂的浓度。本研究通过PVT生长方法制备了3英寸N-B-Al共掺的4H-SiC晶体, 采用Raman光谱、SIMS对晶体的结晶类型和掺杂浓度进行了表征; 采用PL发射谱和激发谱、荧光衰减曲线表征和内量子效率对晶体的发光波长、强度、施主-受主对复合发光性能进行了研究。结果发现, 低浓度Al掺杂样品在室温下发出黄绿色荧光。低浓度Al掺杂在晶体中提供较少的受主; 高浓度B、N掺杂形成施主, 从而贡献充足的电子-空穴对。这些电子-空穴的复合提高了施主-受主对复合的内量子效率, 进而增强光致发光强度, 增加平均发光寿命。     

N掺杂石墨烯量子点的制备及在Fe~(3+)检测中的应用研究

研究了用热解柠檬酸制备发蓝光的石墨烯量子点(GQDs),并在此基础上,用(NH4)2CO3作N源,在水热条件下制备N掺杂石墨烯量子点(N-GQDs)。通过透射电子显微镜(TEM)、X射线光电子能谱仪(XPS)、傅里叶红外光谱仪(FT-IR)、紫外-可见吸收光谱仪(UV-Vis)、荧光光谱仪等对样品的结构和光学性能进行表征。此外,基于荧光淬灭原理,利用N-GQDs构建了一种检测Fe3+的荧光探针。研究表明,N-GQDs的荧光强度随Fe3+浓度的增大而降低,在0~60μmol/L范围内,N-GQDs荧光强度与Fe3+浓度有较好的线性关系,且该探针的检测限低达0.925μmol/L。     

InP量子点的掺杂及其光学性能

采用原位成核掺杂法合成了Li、Zn金属离子掺杂的InP量子点(分别记为Li: InP和Zn: InP), 并研究了掺杂剂对量子点的结构、尺寸和光学性能的影响。研究结果表明, Li⁺、Zn²⁺掺杂的InP量子点结晶度较高且尺寸均匀。虽然Li⁺掺杂未引起InP量子点的结构发生变化, Li⁺未进入InP晶格, 但是抑制了InP量子点的成核与长大, 使其吸收谱和荧光谱均发生大幅度的蓝移。Zn掺杂同样也抑制InP量子点的成核与长大, 并且形成InP/Zn₃P₂/ZnO复合核壳结构, 显著增强了InP量子点的荧光, 尤其是当Zn掺杂浓度(Zn/In原子比)为0.2时, InP量子点的荧光强度增加近100多倍, 这对短波长InP量子点的合成具有一定的参考价值。     

Luminescence of er doped ZnS quantum dots excited by infrared lasers

ZnS:Er quantum dots were prepared in aqueous medium from readily available precursors. The construction, morphology and luminescence properties of the ZnS:Er quantum dots were evaluated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence spectra. The average particle size was calculated using the Scherrer formula to be 4 nm, which is also observed from high resolution transmission electron microscopy (HRTEM) image. Different laser wavelengths at 976 +/- 2 nm and 1480 nm were utilized as the excitation source. ZnS:Er quantum dots had a fluorescence spectrum in 1550 nm region through the 4I13/2 --> 4I15/2 transition. Furthermore, intensity increased with increasing excitation intensity and dopant concentration. The reason for the photoluminescence spectra broadening is discussed. It is because the energy levels of Er3+ are split by a coulombic interaction between electrons, including spin correction and spin-orbit coupling, and eventually by the Stark effect due to ZnS QDs crystal field and local coordination.     

Synthesis and photoluminescence of ZnS quantum dots

Single-phase zinc sulphide (ZnS) quantum dots were synthesized by a chemical method. The influence of the pH value of the Zn(CH3COO)2 solution on the size and photoluminescence properties of the ZnS quantum dots was evaluated. X-ray power diffraction, transmission electron microscopy, and ultraviolet-visible spectroscopy were used to characterize the structure, size, surface states, and photoluminescence properties of ZnS quantum dots. The results showed that the crystal structure of ZnS quantum dots was a cubic zinc blende structure, and their average diameter was about 3.0 nm. ZnS quantum dots with good distribution and high purity were obtained. A strong broad band centered at about 320 nm was observed in the excitation spectrum of ZnS quantum dots. Their emission spectrum peaking at about 408 nm, was due mostly to the trap-state emission. The relative integrated emission intensity of ZnS quantum dots decreased as the pH value of the Zn(CH3COO)2 solution increased, which could be ascribed to the increase in average diameter of the ZnS quantum dots as the pH value of Zn(CH3COO)2 solution increased.     

Direct Observation of sp-d exchange interactions in colloidal Mn2+- and Co2+-doped CdSe quantum dots

The defining attribute of a diluted magnetic semiconductor (DMS) is the existence of dopant-carrier magnetic exchange interactions. In this letter, we report the first direct observation of such exchange interactions in colloidal doped CdSe nanocrystals. Doped CdSe quantum dots were synthesized by thermal decomposition of (Me4N)2[Cd4(SePh)10] in the presence of TMCl2 (TM2+ = Mn2+ or Co2+) in hexadecylamine and were characterized by several analytical and spectroscopic techniques. Using magnetic circular dichroism spectroscopy, successful doping and the existence of giant excitonic Zeeman splittings in both Mn2+- and Co2+-doped wurtzite CdSe quantum dots are demonstrated unambiguously.     

CdSe量子点的制备及荧光性能改善

主要讨论了CdSe量子点的制备及荧光性能的改善.采用水相合成方法制备了CdSe量子点,并用X射线粉末衍射仪对所合成的量子点进行表征,用荧光分光光度计研究了量子点的荧光性质.结果表明,采用样品处理温度的调节和ZnS壳层的包覆能在一定程度上改善CdSe量子点的荧光性能.     

A novel route to photoluminescent, water-soluble Mn-doped ZnS quantum dots via photopolymerization initiated by the quantum dots

We design a photopolymerization, in which Mn-doped ZnS quantum dots (ZnS:Mn(2+)) initiate the polymerization of acrylic acid, to convert the non-cytotoxic quantum dots to water-soluble ones for biological chromophores The prepared quantum dots are nearly monodispersed in water and the resulting solution shows long-term stability for months. The water-soluble ZnS:Mn(2+) quantum dots exhibit high quantum efficiency of fluorescence. The polymerization of acrylic acid is ruled by a free-radical mechanism and results in a polymer with a random configuration. Raman scattering shows that, in the water-soluble quantum dots, the vibration modes of surface optical phonons, transverse optical phonons and longitudinal optical phonons are changed in frequencies. Results of model calculations correlate these changes to the polymerization occurring at the surface of QDs.     

原位聚合法制备聚丙烯酸修饰的ZnS量子点

采用原位聚合法对ZnS量子点表面进行聚丙烯酸(PAA)的修饰。利用XRD、FTIR、TEM、TGA、荧光测试等对ZnS@PAA复合纳米粒子进行系列表征。XRD分析表明,修饰后的ZnS仍为立方晶相。FTIR和TGA结果证明,ZnS纳米粒子表面存在PAA。TEM结果表明,修饰后ZnS@PAA复合纳米粒子在去离子水中分散良好,其直径有所增加,约为28 nm,且呈较明显的核-壳结构。荧光测试发现,修饰PAA前后ZnS@PAA复合纳米粒子的发光特性没有发生明显改变。实验表明,经PAA修饰后,ZnS@PAA复合纳米粒子在水溶液中的分散性和稳定性得到提高,抗氧化性和荧光稳定性也得到了一定的增强。      

Luminescent quantum dots fluorescence resonance energy transfer-based probes for enzymatic activity and enzyme inhibitors

The paper describes the development and characterization of analytical properties of quantum dot-based probes for enzymatic activity and for screening enzyme inhibitors. The luminescent probes are based on fluorescence resonance energy transfer (FRET) between luminescent quantum dots that serve as donors and rhodamine acceptors that are immobilized to the surface of the quantum dots through peptide linkers. Peptide-coated CdSe/ZnS quantum dots were prepared using a one-step ligand exchange process in which RGDC peptide molecules replace trioctylphosphine oxide (TOPO) molecules as the capping ligands of the quantum dots. The peptide molecules were bound to the surface of the CdSe/ZnS quantum dots through the thiol group of the peptide cysteine residue. The peptide-coated quantum dots were labeled with rhodamine to form the FRET probes. The emission quantum yield of the quantum dot FRET probes was 4-fold lower than the emission quantum yield of TOPO-capped quantum dots. However, the quantum dot FRET probes were sufficiently bright to enable quantitative enzyme and enzyme inhibition assays. The probes were used first to test the enzymatic activity of trypsin in solution based on FRET signal changes of the quantum dot-based enzymatic probes in the presence of proteolytic enzymes. For example, exposure of the quantum dot FRET probes to 500 microg/mL trypsin for 15 min resulted in 60% increase in the photoluminescence of the quantum dots and a corresponding decrease in the emission of the rhodamine molecules. These changes resulted from the release of rhodamine molecules from the surface of the quantum dots due to enzymatic cleavage of the peptide molecules. The quantum dot FRET-based probes were used to monitor the enzymatic activity of trypsin and to screen trypsin inhibitors for their inhibition efficiency.     

Effect of swift heavy ion irradiation on bare and coated ZnS quantum dots

The present study compares structural and optical modifications of bare and silica (SiO₂) coated ZnS quantum dots under swift heavy ion (SHI) irradiation. Bare and silica coated ZnS quantum dots were prepared following an inexpensive chemical route using polyvinyl alcohol (PVA) as the dielectric host matrix. X-ray diffraction (XRD) and transmission electron microscopy (TEM) study of the samples show the formation of almost spherical ZnS quantum dots. The UV-Vis absorption spectra reveal blue shift relative to bulk material in absorption energy while photoluminescence (PL) spectra suggests that surface state and near band edge emissions are dominating in case of bare and coated samples, respectively. Swift heavy ion irradiation of the samples was carried out with 160 MeV Ni¹²⁺ ion beam with fluences 10¹² to 10¹³ ions/cm². Size enhancement of bare quantum dots after irradiation has been indicated in XRD and TEM analysis of the samples which has also been supported by optical absorption spectra. However similar investigations on irradiated coated quantum dots revealed little change in quantum dot size and emission. The present study thus shows that the coated ZnS quantum dots are stable upon SHI irradiation compared to the bare one.