CuInS2纳米晶的制备和发光性质

以十二硫醇为溶剂,通过选择合适的金属源制备了各种尺寸的CuInS₂量子点。观察到随着粒子的尺寸减小,其吸收和发光光谱明显蓝移,存在明显的量子尺寸效应。通过在CuInS₂纳米晶表面包覆ZnS壳层,发现随着壳层厚度增加,其发光量子效率明显提高,最大达到了48%;继续增加壳层厚度,其发光量子效率反而降低。进一步测量它们的荧光寿命,发现包覆ZnS壳层后的CuInS₂纳米晶的荧光寿命明显增加,证实表面包覆明显减少其表面的无辐射复合中心,提高了其发光效率。进一步制备了CuInS₂/ZnS核壳量子点发光二极管,并对其电致发光性质进行了研究。     

基于CdSe/ZnS量子点光转化层的高稳定性白光LED器件

采用一步法合成了510,550和630 nm三种峰值的高稳定性、高量子效率核壳结构CdSe/ZnS量子点材料,其量子产率分别达到82%,98%,97%。将该量子点材料取代传统的荧光粉材料,与硅胶均匀混合后作为光转换层涂覆到蓝色InGaN LED芯片上,制备了白光LED器件。通过依次添加不同颜色量子点制备的量子点光转换层,考察了510,550和630 nm三色CdSe/ZnS量子点在硅胶中的不同配比对白光LED器件性能的影响,研究了不同颜色量子点之间的能量转换机制,利用量子点对白光光谱及其色坐标的影响机制,得到优化的白光器件结果及其三色量子点的配比,结果表明,当绿色、黄绿色、红色三种量子点之间的配比为24∶7∶10时,得到高稳定性、高效率的正白光器件特性,在电流20～200 mA范围内,色温变化为4 607～5 920 K,色坐标变化为（0.355 1,0.348 3）～（0.323 4,0.336 1）,显色指数变化为77.6～84.2,器件最高功率效率达到31.69 lm W-1@20 mA。另外,为了进一步考察器件性能稳定的原因,研究了时间、温度以及UV处理对CdSe/ZnS QDs/硅胶混合光转换材料稳定性的影响,结果表明,器件的高稳定性可归因于所采用的一步法合成的核壳结构量子点材料本身的稳定性,研究的优化器件结果是一种低能耗的优质白光光源,可使人们真实地感知物体的原貌,在正白光光源领域具有很好的应用前景。     

铜铟硫纳米晶/PMMA复合薄膜的制备与光学性质表征

铜铟硫(CuInS₂)纳米晶具有发射光谱宽、波长易于调控、量子产率高、合成成本低、容易与封装材料复合等优点,在远程白光LED结构中具有广阔的应用前景。远程白光LED结构是针对LED散热问题提出的一种新型封装结构,在这种结构中复合荧光涂层(复合薄膜)与蓝光芯片进行隔离封装,这种结构对复合薄膜中纳米晶的热稳定性的要求大大降低。首先合成出了不同发光波长的CuInS₂纳米晶荧光材料,然后将其封装到PMMA基质中制备了系列的CuInS₂纳米晶/PMMA复合薄膜。通过荧光光谱和紫外可见光谱的方法,针对纳米晶复合薄膜出现的发光波长红移以及不同发光波长纳米晶/PMMA复合薄膜透过率不一致的现象进行了详细研究。     

核壳型ZnS∶Cu/ZnS量子点的制备及发光性质

本文采用水相合成方法制备了ZnS∶Cu量子点并进行了ZnS壳层修饰,研究了壳层厚度对ZnS∶Cu量子点光学性质的影响,采用TEM、XRD、PL、PLE和UV-Vis等测试方法对其进行了表征。实验结果表明,合成的ZnS∶Cu/ZnS量子点为立方闪锌矿,尺寸分布均匀呈球形,分散性良好,经过壳层修饰平均粒径由2 nm增加到3.2 nm。随着ZnS壳与ZnS核量的比的增加,量子点的PLE激发峰位置和UV-Vis吸收谱线出现红移,也说明了量子点的尺寸增大,证明ZnS在ZnS∶Cu量子点的表面生长,形成了核壳结构的ZnS∶Cu/ZnS量子点。随着壳层增厚,量子点与铜离子发光中心相关的发射峰强度先增大后减小,当壳核比n_s/n_c=2.5时,发光强度达到最大。     

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。     

HgTe/CdS/ZnS多壳层量子点的制备与表征

采用一种简单的方法合成HgTe/CdS/ZnS多壳层量子点。首先,以1-硫代甘油为稳定剂,在水相溶液中制备出HgTe核量子点;然后,采用外延生长法依次在HgTe核量子点表面包覆CdS和ZnS壳层,合成出最终具有稳定近红外发光的HgTe/CdS/ZnS多壳层量子点。该合成方法仅需3个步骤,具有操作简单、成本低廉的优点。实验结果显示,当反应温度为90 ℃、反应溶液pH为11.0、反应加热回流时间为4 min时,HgTe/CdS/ZnS多壳层量子点具有最高荧光量子产率36%。     

ZnSe(ZnS)纳米晶与MEH-PPV的共掺有机电致发光器件

采用水相法合成核壳结构ZnSe/ZnS 纳米晶,经X射线衍射(XRD)分析和透射电子显微镜(TEM)表征,证实所制备的样品为立方晶型闪锌矿结构ZnSe/ZnS量子点。按照一定的质量比将ZnSe/ZnS 纳米晶和有机聚合物MEH-PPV(poly ) 共掺并将其作为发光层,分别制备单层和多层有机电致发光器件,结构为ITO/MEH-PPV∶ZnSe(ZnS)(50 nm)/Al和 ITO/PEDOT∶PSS(70 nm)/ MEH-PPV∶ZnSe(ZnS)(50 nm)/BCP(15 nm)/Alq₃(12 nm) /LiF(0.5 nm)/Al。实验结果表明,多层发光器件的发光特性与单层器件不同,工作电压的增大使其发光峰发生了明显的蓝移。     

半导体量子点在白光LED器件上的应用研究

以CdSe, CuInS₂和CdS:Mn量子点为例, 本文基于量子点白光LED器件的电光转换过程, 引入量子点的“类”光谱光效率函数, 给出了该器件的色坐标、光效和量子点配比等计算公式, 理论计算结果和实验结果基本一致. 研究结果表明量子点的荧光峰位和峰宽对白光器件的显色指数有显著影响.     

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。     

ZnO作为电子传输层的绿光胶体CdSe量子点LED(QD-LED)的制备与表征

通过调节作为发光层的量子点的尺寸,可以制作出覆盖可见光(380～780 nm)以及近红外光谱的量子点LED(QD-LED),其光谱范围很窄且半高宽可达30 nm。然而量子点LED的寿命、亮度以及效率需要进一步提高才能满足商业化的需求。为了研究QD-LED器件的特性,本文采用523 nm波长的CdSe/ZnS核壳型量子点为发光层、poly-TPD为空穴传输层、ZnO为电子传输层,制备了绿光量子点LED,并表征了器件的特性。     

ZnO/ZnS核-壳量子点的双光子吸收效应

利用飞秒激光Z-扫描与泵浦-探测技术,研究了室温下ZnO/ZnS与ZnO/ZnS/Ag核-壳胶体量子点的双光子吸收效应.研究发现:ZnO基核-壳量子点的本征双光子吸收系数比ZnO体材料增大了3个数量级;测量得到的660 nm处的ZnO/ZnS核-壳量子点双光子吸收截面约为4.3×10^-44 cm⁴·s·photon^-1,比相应的ZnS、ZnSe及 CdS量子点大2个数量级;当ZnO/ZnS核-壳量子点镶嵌了银纳米点时,非线性吸收有所增强.ZnO基复合纳米结构的双光子吸收增强可归因于量子限域与局域场效应.     

ZnCuInS/ZnSe/ZnS量子点发光光谱特性的研究

ZnCuInS/ZnSe/ZnS量子点是一种无毒,无重金属的“绿色”半导体纳米材料。在研究中,制备了三种尺寸的ZnCuInS/ZnSe/ZnS核壳量子点,其直径分别为3.3,2.7,2.3 nm。通过测量不同尺寸的ZnCuInS/ZnSe/ZnS量子点的光致发光光谱,其发射峰值波长随尺寸的减小而蓝移。其吸收峰值波长和发射峰值波长分别是510,611(3.3 nm),483,583(2.7 nm)以及447,545 nm(2.3 nm)。ZnCuInS/ZnSe/ZnS量子点具有显著的尺寸依赖效应。ZnCuInS/ZnSe/ZnS量子点的斯托克斯位移分别为398 meV(3.3 nm),436 meV(2.7 nm)以及498 meV(2.3 nm),这样大的斯托克斯位移证明,ZnCuInS/ZnSe/ZnS量子点的发光机制与缺陷能级有关。同时,对直径为3.3 nm的ZnCuInS/ZnSe/ZnS量子点进行了温度依赖的光致发光光谱的测量,当温度为15～90 ℃时,该量子点发射峰值波长随温度的升高而红移,发光强度随温度的升高而降低,说明ZnCuInS/ZnSe/ZnS量子点是以导带能级与缺陷能级之间跃迁为主的复合发光。     

ZnCuInS/ZnS量子点与Poly-TPD补偿发光光谱的研究

ZnCuInS/ZnS量子点是一种无重金属、“绿色”半导体纳米材料。在研究中,制备出尺寸为3.2 nm的ZnCuInS/ZnS核壳量子点,并说明它是施主-受主对复合发光。通过测量ZnCuInS/ZnS量子点的光致发光光谱,其发射峰值波长为620 nm、半宽度是95 nm的红光。同时,还制备出Poly-TPD有机薄膜,其发光光谱是峰值波长为480 nm的蓝光。所以,ZnCuInS/ZnS量子点和Poly-TPD发光颜色具有互补性。在ZnCuInS/ZnS量子点薄膜层上包覆一层poly-TPD薄膜后,二者发光颜色互补。在恰当的偏置电压下,可以得到较好的白光光谱。计算表明,其色坐标是(0.336,0.339),颜色指数是92。     

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。     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Stability and luminescence properties of CsPbBr3/CdSe/Al core-shell quantum dots

To improve the stability and luminescence properties of CsPbBr₃ QDs, we proposed a new core-shell structure for CsPbBr₃/CdSe/Al quantum dots (QDs). By using a simple method of ion layer adsorption and a reaction method, CdSe and Al were respectively packaged on the surface of CsPbBr₃ QDs to form the core-shell CsPbBr₃/CdSe/Al QDs. After one week in a natural environment, the photoluminescence quantum yields of CsPbBr₃/CdSe/Al QDs were greater than 80%, and the PL intensity remained at 71% of the original intensity. Furthermore, the CsPbBr₃/CdSe/Al QDs were used as green emitters for white light-emitting diodes (LEDs), with the LEDs spectrum covering 129% of the national television system committee (NTSC) standard color gamut. The core-shell structure of QDs can effectively improve the stability of CsPbBr₃ QDs, which has promising prospects in optoelectronic devices.     

红、绿CdSe@ZnS量子点配比对三波段标准白光LED器件的影响

将一步法合成的具有梯度合金结构的红光、绿光CdSe@ZnS量子点与硅胶均匀混合后,作为光转换层涂覆到蓝色InGaN LED芯片上,制备了不含荧光材料的三波段白光LED器件。研究了峰值为650 nm和550 nm的高效率红、绿量子点在硅胶中的含量及配比对白光LED色坐标以及效率的影响。结果表明,当红、绿量子点配比为2：3时,可得到发射纯正白光的QDs-LED器件,色坐标为（0.322 8,0.335 9）、色温为5 725 K,功率效率为26.61 lm/W,显色指数为72.7。光谱中红、蓝、绿三色发光峰的半高宽分别为30,25,38 nm,表明器件具有很好的单色性和高色纯度。     

Effect of the Semiconductor Quantum Dot Shell Structure on Fluorescence Quenching by Acridine Ligand

The main line of research in cancer treatment is the development of methods for early diagnosis and targeted drug delivery to cancer cells. Fluorescent semiconductor core/shell nanocrystals of quantum dots (e.g., CdSe/ZnS) conjugated with an anticancer drug, e.g., an acridine derivative, allow real-time tracking and control of the process of the drug delivery to tumors. However, linking of acridine derivatives to a quantum dot can be accompanied by quantum dot fluorescence quenching caused by electron transfer from the quantum dot to the organic molecule. In this work, it has been shown that the structure of the shell of the quantum dot plays the decisive role in the process of photoinduced charge transfer from the quantum dot to the acridine ligand, which is responsible for fluorescence quenching. It has been shown that multicomponent ZnS/CdS/ZnS shells of CdSe cores of quantum dots, which have a relatively small thickness, make it possible to significantly suppress a decrease in the quantum yield of fluorescence of quantum dots as compared to both the classical ZnS thin shell and superthick shells of the same composition. Thus, core/multicomponent shell CdSe/ZnS/CdS/ZnS quantum dots can be used as optimal fluorescent probes for the development of systems for diagnosis and treatment of cancer with the use of anticancer compounds based on acridine derivatives.     

Preparation of Highly Stable and Photoluminescent Cadmium-Free InP/GaP/ZnS Core/Shell Quantum Dots and Application to Quantitative Immunoassay

Indium phosphide (InP) quantum dots (QDs) are ideal substitutes for widely used cadmium-based QDs and have great application prospects in biological fields due to their environmentally benign properties and human safety. However, the synthesis of InP core/shell QDs with biocompatibility, high quantum yield (QY), uniform particle size, and high stability is still a challenging subject. Herein, high quality (QY up to 72%) thick shell InP/GaP/ZnS core/shell QDs (12.8 ± 1.4 nm) are synthesized using multiple injections of shell precursor and extension of shell growth time, with GaP serving as the intermediate layer and 1-octanethiol acting as the new S source. The thick shell InP/GaP/ZnS core/shell QDs still keep high QY and photostability after transfer into water. InP/GaP/ZnS core/shell QDs as fluorescence labels to establish QD-based fluorescence-linked immunosorbent assay (QD-FLISA) for quantitative detection of C-reactive protein (CRP), and a calibration curve is established between fluorescence intensity and CRP concentrations (range: 1–800 ng mL⁻¹, correlation coefficient: R² = 0.9992). The limit of detection is 2.9 ng mL⁻¹, which increases twofold compared to previously reported cadmium-free QD-based immunoassays. Thus, InP/GaP/ZnS core/shell QDs as a great promise fluorescence labeling material, provide a new route for cadmium-free sensitive and specific immunoassays in biomedical fields.