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。     

核壳结构硒化镉/硫化镉/巯基乙酸量子点载流子输运特性

采用水溶液法合成了巯基乙酸(TGA) 包覆的CdSe 量子点. 通过X 射线粉末衍射和高分辨透射显微镜检测结果证实, 合成得到闪锌矿结构CdSe 量子点. 能谱图和傅里叶变换红外光谱图结果说明, 在核CdSe 纳米粒子表面与配体TGA 之间有CdS 壳层结构形成. 利用样品表面光电压(SPV) 谱, 指认CdSe 量子点精细能带结构以及各自对应的激发态特征: 475 nm (2.61 eV) 和400 nm (3.1 eV) 两个波长处的SPV 响应峰分别与CdSe 核和CdS 壳层带-带隙跃迁相对应; 370 nm (3.35 eV) 附近SPV 响应峰可能与TGA 中羰基与巯基或羧基之间发生的n →π^* 跃迁有关. 场诱导表面光电压谱结果证实, 合成的CdSe 量子点具有明显的N 型表面光伏特性, 而上述n→π^* 跃迁则具有P 型表面光伏特性. 荧光光谱谱线均匀增宽以及SPV 响应峰位蓝移, 说明样品具有明显的量子尺寸效应. 结合不同pH 值下合成的CdSe 量子点的SPV 谱和表面光声谱发现, SPV 响应强度与表面光声光谱信号强度变化趋势恰好相反. 上述样品表面光伏效应表明, CdSe 量子点表面和相界面处的精细电子结构以及光生载流子的输运特性均与量子点的尺寸大小存在某种内在联系. 关键词： 硒化镉量子点 光生载流子 表面光电压谱 表面光声光谱     

复合荧光CdSe量子点-脂质体的制备与表征

通过脂质体方法成功地将三辛基氧化膦(TOPO)包覆的CdSe发光量子点从非极性有机溶剂转移到生物相容性的水溶液中.分别通过透射电镜(TEM)、荧光Mapping图像,以及光致发光(PL)光谱进行表征.TEM照片显示制备的CdSe核量子点为球形,具有良好的单分散特性,平均粒径约为3nm.CdSe-脂质体复合体的平均尺寸大约20nm,TEM清楚地显示了CdSe量子点被诱捕在脂质体中.荧光Mapping显示了CdSe-脂质体复合体的发光强度分布.脂质体方法转移TOPO包覆的CdSe量子点,借助了磷脂的双分子链与CdSe表面的TOPO配体之间的疏水相互作用,在CdSe的第一配体层外部形成第二配体层,保留了CdSe的存在环境,光致发光光谱表明,量子点-脂质复合体基本保持了CdSe核量子点的发射效率.     

壳层相关的CdSe核/壳量子点发光的热稳定性

测量了CdSe/ZnS(3 ML)核/壳结构及CdSe/CdS(3 ML)/ZnCdS(1 ML)/ZnS(2 ML)核/多壳层结构量子点在80~460 K范围内的光致发光光谱,研究了壳层结构对CdSe量子点发光热稳定性的影响。详细地分析了CdSe量子点的发光峰位能量、线宽和积分强度与温度之间的关系,发现CdSe量子点的发光热稳定性依赖于壳层结构。CdS/ZnCdS/ZnS多壳层结构包覆CdSe量子点在低温和高温部分的热激活能均大于ZnS壳层包覆的CdSe量子点,具有更好的发光热稳定性。此外,在300-460-300 K加热-冷却循环实验中,CdS/ZnCdS/ZnS多壳层结构包覆CdSe量子点的发光强度永久性损失更少,热抵御能力更强。     

谷胱甘肽包被的CdSe/CdS量子点的直接水相制备及其对人血淋巴细胞的标记成像

首次用谷胱甘肽(GSH)作为稳定剂,在水溶液中制备了稳定地发射绿色荧光和橙色荧光的两种 CdSe/CdS核/壳结构的纳米量子点。用紫外-可见分光光度和荧光光谱方法研究了CdSe/CdS量子点的发光特性。透射电镜(TEM)结果表明CdSe/CdS量子点近似球形,在水中分散性良好,比CdSe量子点具有更优异的发光特性,发射光谱和吸收光谱都有红移现象。将CdSe/CdS量子点与鼠抗人CD3抗体连接,制备了水溶性CdSe/CdS-CD3复合物探针,对人血淋巴细胞进行标记和成像。结果表明用该探针对人血淋巴细胞成像清晰,其荧光在30 min的连续蓝光激发下无明显衰退,而FITC荧光在20 min内基本完全猝灭。     

CdSe/CdS核壳量子点复合材料合成及其在白光发光二极管中的应用

采用有机化学合成法,利用正三辛基膦(TOP)辅助的快速注入生长方法,改进传统的制备工艺,实现了CdSe/CdS厚壳层核壳(8.6 ML)量子点复合材料的合成制备,并对所合成的核、核壳量子点及其复合材料的晶格结构、形貌特点与发光性质进行了XRD、TEM、SEM、UV-Vis、PL表征和红光补偿效果测试。测试结果表明,CdSe核具有立方纤锌矿晶格结构;CdSe/CdS量子点复合材料直径为45~75μm,呈菱形规则形貌,且颗粒分散性良好。采用该方法,可以提高量子产率,产率由4%(CdSe核)升至48%(CdSe/CdS核壳量子点);可以增强激子态发光能力,CdSe/CdS核壳量子点复合材料的荧光强度约为CdSe核的13倍。将该材料与YAG∶Ce~(3+)黄色荧光粉组合应用,获得了高光效(148.29 lm/W)、高显色指数(Ra为90.1,R9为97.0)的白光发光二级管,表明按照上述方法获得的CdSe/CdS核壳量子点复合材料在白光发光二极管中深红光波段具有较好的补偿效果。     

CdSe/CdS/ZnS量子点光纤的增益研究

采用油相法合成了CdSe/CdS/ZnS量子点,相对于CdSe量子点,其吸收光谱、发射光谱均发生了红移。利用COMSOL Multiphysics软件模拟CdSe/CdS/ZnS量子点光纤和甲苯光纤的电场分布,结果表明CdSe/CdS/ZnS量子点光纤的电场强度高于甲苯光纤。采用中心波长为532 nm的稳态半导体激光器作为光源,对甲苯光纤、CdSe/ZnS量子点光纤、CdSe/CdS/ZnS量子点光纤进行电压信号测试,发现CdSe/ZnS量子点光纤和CdSe/CdS/ZnS量子点光纤的电压信号值相对于甲苯光纤电压信号值分别增强了6.28 mV和18.43 mV,表明双壳型量子点光纤的增益高于单壳型量子点。     

CdSe量子点膨润土复合材料的制备与表征

首先以CdCl₂·2.5H₂O、SeO₂和NaBH₄为反应物,制备巯基丁二酸稳定的CdSe量子点。然后将有机膨润土与CdSe量子点溶液混合并充分搅拌,制备负载CdSe量子点的膨润土发光材料,用荧光光谱、扫描电镜和X射线粉末衍射等分析测试手段对所得材料的光谱性能与微观结构进行表征。光谱分析表明,量子点膨润土复合材料的发光颜色与量子点溶液非常一致;X射线光电子能谱分析表明,复合后的材料中含有Cd 和 Se两种元素;此外,在量子点膨润土复合材料X射线粉末衍射谱中可见CdSe量子点（111）、（220）及（331）3个晶面的衍射峰,2θ=4.3°处出现膨润土（001）衍射峰。数据表明,在制备的CdSe量子点膨润土复合材料中,量子点和膨润土的结构都没有改变。     

巯基丙酸分子对CdSe核壳量子点和 ZnO纳米粒子薄膜之间电荷转移的影响

通过稳态光谱和时间分辨荧光光谱研究了巯基丙酸(MPA)分子对由量子点到ZnO纳米粒子薄膜的电荷转移过程的影响。研究发现,相对于CdSe纳米粒子薄膜样品,没有MPA分子参与作用的CdSe/ZnO薄膜样品和有MPA分子连接的CdSe/MPA/ZnO薄膜样品中都存在从CdSe量子点到ZnO纳米粒子薄膜的有效电荷分离过程,但是相对于CdSe/ZnO样品, CdSe/MPA/ZnO样品中电荷转移速率明显变小。这表明MPA分子本身它并不能促进CdSe到ZnO电荷分离过程,因此可以认为用金属氧化物薄膜直接吸附量子点吸收材料,将能获得高功率转换效率的量子点敏化太阳能电池。     

脂溶性CdSe/ZnS量子点脂质体复合物的制备及表征

在油相中成功合成了脂溶性CdSe/ZnS核壳量子点纳米粒,粒径平均为4.5 nm,量子产率达29%,发射波长为540 nm。通过薄膜分散法,以蛋黄卵磷脂、胆固醇为膜材,将脂溶性的CdSe/ZnS核壳量子点包覆于脂质体磷脂双分子层中,由于磷脂分子的两亲性,使得脂溶性的CdSe/ZnS核壳量子点同时又具有亲水性。通过透射电镜对脂质体形态进行了表征,倒置荧光显微镜证实了发光CdSe/ZnS核壳量子点成功包埋于脂质体双分子层中,包裹的发光CdSe/ZnS核壳量子点具有更稳定的发光及抗光漂白性质。     

Encapsulation of highly confined CdSe quantum dots for defect free luminescence and improved stability

This is the first report on the generation of trap states and their effective elimination in highly confined CdSe quantum dots in order to obtain enhanced and stable optical properties prepared by aqueous route. Surface plays an important role in optical properties of quantum dots (QDs) and surface modification of quantum dots can improve optical properties. In present work luminescent CdSe QDs were prepared using 2-Mercaptoethanol (2-ME) as stabilizing agent and encapsulated by polymer. Different concentrations of 2-ME were used to tune the emission spectra with respect to their reduced size. Addition of 2-ME to CdSe QDs enhances the trap emission and quenching band edge emission due to (i) increased surface to volume ratio and; (ii) presence of high concentration of sulfide ions as confirmed from EDX analysis as sulfide ions possesses the hole scavenging characteristics. Polymer encapsulation of QDs was carried out to make them stable and to improve their optical properties. Even though there are previous reports addressing the improved optical properties by polymer encapsulation and silica encapsulation but experimentally it has not been reported yet experimentally. In this work we have synthesized and characterized water soluble polymer encapsulated QDs and proved the facts experimentally. Photoluminescence spectroscopy clearly reveals the role of polymer encapsulation in boosting the optical properties of CdSe QDs. FTIR spectra validate the presence of biocompatible functional groups on CdSe4/PEG (Polymer encapsulated QDs).     

胶体CdSe量子点的色度学特性研究

使用化学胶体法合成了CdSe量子点，研究了样品的荧光量子产率，发现随CdSe量子点粒径的增大，荧光量子产率存在先增大后减小的现象.研究了CdSe量子点的色度学特性，通过对不同尺寸、不同粒径分布范围的CdSe量子点色度坐标的计算，讨论了粒径分布范围对其荧光颜色饱和度的影响，解释了为何难以获得高颜色饱和度的绿光量子点.利用红、蓝两种不同尺寸的量子点配制出白光样品，提出了估计配色后样品色度坐标的经验公式，结果显示白光样品色度坐标的实验值与经验公式估计值基本一致.     

CdSe/ZnS电化学发光法测定去甲肾上腺素

以巯基丙酸为稳定剂制备了水溶性CdSe/ZnS量子点,并采用滴涂法制备了CdSe/ZnS修饰的金电极（CdSe/ZnS/GE）,研究其电化学发光（ECL）性质,考察了pH、CdSe/ZnS浓度、扫描速度、静置时间等实验条件对ECL强度的影响。结果表明,在碱性溶液中,去甲肾上腺素（NE）在鲁米诺溶液中对CdSe/ZnS的电化学发光信号有明显的增敏作用,由此建立了一种检测去甲肾上腺素的新方法。当去甲肾上腺素的浓度（C_NE）在2.3×10^-5~1.0×10^-8 mol/L范围内时,去甲肾上腺素的浓度与相对电化学发光强度呈现良好的线性关系。线性回归方程为ΔI_ECL=118.788C_NE-15.333（R=0.994 4）,最低检测限（S/N=3）为0.33×10^-8 mol/L。     

Zeeman mapping of exciton localization in self-assembled CdSe quantum dots using diluted magnetic semiconductors

Localization of exciton wavefunctions in self-assembled quantum dots (QDs) has been investigated using CdSe QDs embedded in ZnMnSe. This system was chosen so as to make use of the giant Zeeman splitting in the diluted magnetic semiconductor (DMS) ZnMnSe, which enables one to map how the exciton wavefunction is distributed between the QDs and the surrounding matrix. Two series of CdSe QDs in ZnMnSe were prepared for this investigation by molecular beam epitaxy (MBE), either by varying the CdSe coverage while keeping a constant Mn concentration in ZnMnSe; or by varying the Mn concentration in the matrix while maintaining a constant CdSe coverage. Photoluminescence (PL) experiments show a systematic evolution of the CdSe QDs with increasing CdSe coverage; and also reveal the role of Mn in nucleating (“seeding”) the self-assembly of the QDs. By simultaneously measuring the Zeeman shifts of the PL peaks from both the CdSe QDs and their ZnMnSe matrix, we are able to extract information on exciton localization in the QDs and its dependence on the degree of development of the self-assembled CdSe QDs with increasing CdSe coverage.     

CdSe/ZnSe/ZnS多壳层结构量子点的制备与表征

展示了一种简捷的多壳层量子点合成路线。在含有过量Se源的CdSe体系中直接注入Zn源,"一步法"合成了CdSe/ZnSe量子点;进一步以CdSe/ZnSe为"核",表面外延生长ZnS壳层制备了核/壳/壳结构CdSe/ZnSe/ZnS量子点。相对于以往报道的多壳层结构量子点的制备方法,该方法通过减少壳层的生长步骤有效地简化了实验操作,缩短了实验周期,同时减少对原料的损耗。对量子点进行高温退火处理,能够大幅提高CdSe/ZnSe/ZnS量子点的发光量子产率。透射电镜、XRD以及光谱研究表明:所制备的量子点接近球形,核与壳层纳米晶均为闪锌矿结构,最终获得的CdSe/ZnSe/ZnS量子点的光致发光量子产率达到53％。为了实现量子点的表面生物功能化,通过巯基酸进行了表面配体交换修饰,使量子点表面具有水溶性的羧基功能团,并且能够维持较高的光致发光量子产率。     

Synthesis,biocompatibility and luminescence properties of quantum dots conjugated with amino acid-functionalized β-cyclodextrin

A series of CdSe and CdSe/CdS quantum dots (QDs) labeled with amino acid-modified β-cyclodextrin (β-CD) was prepared by a simple ultrasonic method. These amino acid-modified β-CD-coated QDs are very soluble and stable in biological buffer. They also have high colloidal stability and strong optical emission properties that are similar to those of untreated tri-n-octylphosphine oxide (TOPO)-coated QDs. The quantum yields (QYs) of these amino acid-modified β-CD-coated CdSe and CdSe/CdS QDs in biological buffer were found to be very high. In particular, the QYs of the positively charged l-His-β-CD-coated CdSe/CdS QDs were as high as 33.5±1.8%. In addition, the fluorescence lifetime of these QDs was also very long in PBS solutions as determined by frequency domain spectroscopy. For example, the lifetime of l-His-β-CD-coated CdSe/CdS QDs was 8.6 ns. The in vitro cytotoxicity of these QDs in ECV-304, SH-SY5Y and HeLa cells was found to be lower. l-His-β-CD-coated CdSe/CdS QDs were the least cytotoxic (IC₅₀ 95.6±3.2 mg mL^?1 in ECV-304 cells after 48 h). The flow cytometry results show that the positively charged amino acid led to a considerable increase in biocompatibility of QDs. This may be attributed to the presence of an amino acid-modified β-CD outer layer, which enhanced the biocompatibility.     

Silica-coated quantum dots fluorescent spheres synthesized using a quaternary ‘water-in-oil’ microemulsion system

Nanoscale and microscale silica spheres embedded with multiple CdSe quantum dots (QDs, having average diameters of about 2.4 and 5.0 nm, respectively.) were synthesized by using a quaternary ‘water-in-oil’ microemulsion. Comparing the uncoated QDs, the quantum yields (QYs) of the silica-coated QD spheres were enhanced when the QD cores were synthesized using mercaptoacetic acid (MA) as a stabilizer, while the QYs were dramatically decreased when the cores were synthesized using citric acid (CA) as a stabilizer. The enhanced QYs could be further improved by heating the silica-coated QDs in aqueous solution. Although the QYs of the silica-coated QDs were not high, these spheres emitted bright fluorescence. The silica shells contained numerous micropores (∼0.58–0.91 nm), and small amounts of toxic ions (such as Cd²⁺) could be released from the silica spheres. However, the release rate of toxic ions from the silica spheres was significantly reduced compared with that of the uncoated QDs.     

不同厚度CdSe阱层的表面上自组织CdSe量子点的发光性质

利用变温和变激发功率分别研究了不同厚度CdSe阱层的自组织CdSe量子点的发光。稳态变温光谱表明:低温下CdSe量子阱有很强的发光,高温猝灭,而其表面上的量子点发光可持续到室温,原因归结于量子点的三维量子尺寸限制效应;变激发功率光谱表明:量子点激子发光是典型的自由激子发光,且在功率增加时。宽阱层表面上的CdSe量子点有明显的带填充效应。通过比较不同CdSe阱层厚度的样品的发光,发现其表面上量子点的发光差异较大,这可以归结为阱层厚度不同导致应变弛豫的程度不同,直接决定了所形成量子点的大小与空间分布^[1]。