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。     

Highly luminescent (ZnSe)ZnS core-shell quantum dots for blue to UV emission: synthesis and characterization

We synthesized nearly monodisperse bare ZnSe nanocrystallites having luminescence which ranges in wavelength from 340 to 430 nm via nucleation due to supersaturation and growth followed by size selective precipitation. Bare ZnSe dots' outermost surface is passivated with organic HDA/TOP. In order to enhance the radiative emission from the semiconductor nanocrystals, we capped the bare ZnSe quantum dots with ZnS semiconductor materials of a wider band gap and 5% of lattice mismatch and produced highly luminescent core-shell (ZnSe)ZnS quantum dots. The core-shell (ZnSe)ZnS nanocrystals show 20 times or more as greatly enhanced luminescence quantum yields as those of bare ZnSe nanocrystals. The ZnSe bare dots and the (ZnSe)ZnS core-shell dots have cubic zinc blende structures as expected from the bulk structure. The observed shapes of bare ZnSe and core-shell (ZnSe)ZnS dots are nearly spherical or ellipsoidal with the aspect ratios of 1.2 and 1.4, respectively. They are not faceted.     

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。     

Photoinduced relaxation processes in self-assembling complexes from CdSe/ZnS water-soluble nanocrystals and cationic porphyrins

Particular features and quenching mechanisms of exciton luminescence of water-soluble nanocomposites that are formed as a result of the interaction of surface charged semiconductor quantum dots (QDs) CdSe/ZnS (d _CdSe = 2.8 nm) and cationic porphyrins (H₂TMPyrP⁴⁺ and ZnTMPyrP⁴⁺) have been studied theoretically and experimentally. It has been found that, in CdSe/ZnS??Porphyrin conjugates, there occurs long-range inductive resonance electronic excitation energy transfer from surface modified (with thioglycolic or mercaptoundecanoic acid) QDs to porphyrins, which is accompanied by quenching of the exciton luminescence of QDs and an increase in the fluorescence intensity of porphyrin. It has been shown that, when mercaptoundecanoic acid is used as a QD shell, the QD luminescence quenching efficiency by porphyrins follows the F?rster-Galanin theory and depends on the overlap integral between the CdSe/ZnS luminescence band and the absorption spectra of free-base porphyrin H₂TMPyrP⁴⁺ and its metal complex ZnTMPyrP⁴⁺. It has been revealed that, as the QDs ? Zn-porphyrin intercenter distance decreases from 39.1 (mercaptoundecanoic acid) to 30.1), a considerable QD luminescence quenching is observed; however, the energy transfer efficiency substantially decreases, from 55% in the former case to 23% in the latter one. Based on the spectral-luminescent data and quantum-chemical calculations, it has been found that the chemical change of H₂TMPyrP⁴⁺ in the structure of the complex with CdSe/ZnS QDs passivated by thioglycolic or mercaptoundecanoic acid is caused by the formation of a metal complex ZnTMPyrP⁴⁺. Based on calculations of the redox-potentials, it has been concluded that the low luminescence quantum yield of CdSe/ZnS QDs passivated by residues of mercaptocarboxylic acids S^?(CH₂) _n COO^? and its dependence on the number of CH₂ groups are related to the possibility of photoinduced electron transfer from the HOMO of passivating molecules to QDs (QD* ? S^?(CH₂)nCOO^? hole transfer). It has been shown that the quenching of the exciton luminescence of QDs in heterogeneous structures CdSe/ZnS(thioglycolic acid)??ZnTMPyrP⁴⁺, which is complementary to the energy transfer, can be caused by the photoinduced electron transfer that involves the participation of the LUMO of the ZnTMPyrP⁴⁺ molecule (QD* ? ZnTMPyrP⁴⁺).     

基于CuInS2/ZnS核壳结构量子点的高光效暖白光LED

采用逐步热注射法合成了用于白光LED的CuInS₂/ZnS(CIS/ZnS)核壳结构量子点.通过调整Cu/In的比率, 在CuInS₂(CIS)量子点的基础上, 合成了发射波长在570~650 nm之间可调的CIS/ZnS量子点.与CIS量子点的低量子产率相比, 具有核壳结构的CIS/ZnS量子点的量子产率达到了78%.通过在黄光荧光粉YAG :Ce³⁺表面旋涂CIS/ZnS量子点的方式制备了暖白光LED器件.在工作电流为10 mA时, 暖白光LED的发光效率达到了244.58 lm/W.由于CIS/ZnS量子点的加入, 所制备的白光LED器件的显色指数达到86.7且发光颜色向暖色调发生了转移, 相应的色坐标为(0.340 6, 0.369 0).     

ZnSe、ZnS量子点的可控合成与表征

采用改进后的合成方法,以Se和ZnO粉末为原料,在十六胺(HDA)、月桂酸(LA)和三辛基膦(TOP)有机溶剂体系中合成了胶体ZnSe和ZnS量子点。主要研究了溶剂配比、反应温度及生长时间对ZnSe量子点粒径和光学性质的影响。结果表明:制得的ZnSe和ZnS量子点均是纤锌矿型结构,且具有较好的尺寸均匀性、分散性及荧光特性。粒子直径可控制在4.5~8 nm范围内。采用参数n(ZnO) : n(HDA) : n(LA)=1 : 2.1 : 5.2,c(TOPSe)=1 mol/L,在280 ℃成核,240 ℃生长条件下合成的ZnSe量子点具有最佳的尺寸范围,并且随着生长时间的延长,粒径变大,荧光发射峰明显红移。     

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.     

Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media

3-Mercaptopropionic acid-capped core/shell ZnS:Cu/ZnS and ZnS:Mn/ZnS doped quantum dots (QDs) prepared through hydrothermal methods exhibit high photoluminescence intensity as well as good photostability. These water-dispersible nanoparticles exhibit high fluorescence sensitivity to folic acid due to the high affinity of the carboxylate groups and nitrogen atoms of folic acid towards the Zn surface atoms of the doped dots. Quenching of the fluorescence intensity of the QDs allows the detection of folic acid concentrations as low as 11 μM, thus affording a very sensitive system for the sensing of this biologically active molecule in aqueous solution. The possible quenching mechanism is discussed.     

Photostability of luminescent water-soluble cadmium selenide nanocrystals with chemical surface modification

We have developed a method for solubilization of hydrophobic CdSe/ZnS nanocrystals of the core/shell type, obtained by high-temperature synthesis in coordinating organic solvents. The method is based on chemical modification of the surface of the nanocrystals with hydrophilic organic mercapto compounds. We have observed that long-chain mercaptoundecanoic acid molecules effectively protect the surface of CdSe/ZnS nanocrystals in water, increasing (compared with short-chain molecules) the photostability of the nanocrystals. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 506–509, July–August, 2006.     

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。     

ZnSe／ZnS多量子阱激子光学双稳性

用MOCVD在CaF_2衬底上生长的ZnSe/ZnS多量子阱材料,在77K下用N_2激光泵浦染料获得的宽带光脉冲进行了非线性光学测量,首次观察到ZnSe/ZnS多量子阱的激子光学双稳性,据分析这是由激子的能带增宽效应引起的增强吸收光学双稳性.     

Intermediate intensity levels during the emission intermittency of single CdSe/ZnS quantum dots

We report on an intermediate intensity level in the emission intermittency of single CdSe/ZnS core shell quantum dots, which has been overlooked in previous experiments most likely due to its low quantum efficiency. The intermediate intensity level is observed in CdSe/ZnS quantum dots of large diameter (about 5 nm diameter) and appears to be independent of the general dark state power law dynamics. The dim emission periods are found to be exponentially distributed and thus correspond to similar findings in CdSe/CdS quantum dots, where their existence has been interpreted in terms of the emission of a positively charged trion.     

基于Mn掺杂ZnS量子点-BSA纳米复合材料检测头孢曲松钠

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法合成了具有优良光学性质的Mn掺杂ZnS量子点。该量子点在室温条件下即可发射较强的磷光信号。将量子点与牛血清蛋白(BSA)偶联后,形成了纳米复合材料。由于BSA对量子点表面缺陷进行了有效修复,量子点发出的磷光明显增强。当加入头孢曲松钠后,头孢曲松钠与BSA的相互作用使量子点的磷光被有效猝灭,该磷光猝灭量(△P)与头孢曲松钠的浓度在一定范围内呈良好的线性关系(R=0.99)。量子点与BSA偶联的最佳条件为:pH=7.4,反应温度37 ℃,反应时间40 min,BSA浓度80 mg·L^-1,量子点浓度40 mg·L^-1。反应形成新的生物纳米复合材料,作为头孢曲松钠的磷光探针,其线性范围为0~30 μmol·L^-1,相关系数R=0.99,检出限为0.14 μmol·L^-1,相对标准偏差为1.63%。     

基于谷胱甘肽配体的ZnSe量子点对pH响应的时间分辨荧光光谱特性

当前,有关量子点pH响应方面的研究主要集中在含Cd（镉）类量子点,且都是研究其稳态荧光光谱对pH值的响应。然而,Cd类量子点对生物体系具有一定的毒性,且稳态荧光光谱法由于受浓度等因素的影响具有一定的不稳定性,因此应用于生物体系中作为pH探针具有明显的缺点。基于以上分析,通过水相合成法,我们制备出了基于谷胱甘肽配体的水溶性ZnSe量子点,该量子点具有毒性小,生物兼容性好等特点,适合被应用于生物体系中。利用所制备的ZnSe量子点,采用时间相关单光子计数技术,结合紫外可见吸收光谱和稳态荧光光谱,对pH值在5~11不同环境下的ZnSe量子点荧光动力学进行了系统性的研究。ZnSe量子点荧光衰减具有两个寿命组分,拟合得到分别为4和24 ns。通过采集不同探测波长下ZnSe量子点荧光衰减曲线,发现其长寿命组分随探测波长的增加而增加,而短寿命组分基本不随探测波长的改变而改变,结合有关报道分析判断,短寿命和长寿命组分分别来源于核内非局域载流子复合和表面态局域载流子复合。实验发现,处于不同pH值的环境下的ZnSe量子点具有不同的荧光寿命,其荧光寿命与pH值的变化呈负相关。通过比较ZnSe量子点两种荧光寿命组分随pH值的变化关系,发现ZnSe量子点的荧光寿命对pH值的响应主要来源于长寿命组分即表面态寿命,且在不同pH值范围内响应的灵敏度不同,在6~8的pH值范围内响应最为显著,表现为长寿命组分随pH值的增加出现一个较大幅度的衰减。实验进一步发现,ZnSe量子点两个寿命组分的比值在不同pH值范围内具有较好的线性相关性,但在不同pH值范围内斜率不同,通过比较,最大值在pH值为6~8的范围内。另外,与金属钠离子相互作用实验及相关报道表明,金属离子对ZnSe量子点荧光寿命的影响较小。以上研究表明,ZnSe量子点在生物体系pH值检测中具有良好的应用前景。     

Successful growth of two different quantum dots on one substrate

We report the successful growth of ZnSe and ZnTe quantum dots (QDs) embedded in ZnS on GaAs substrate. These QDs have good optical properties and show quantum confinement effect. High-resolution electron scanning microscope studies show that these QDs are grown in Volmer–Weber mode. It is found that the size of the QDs is controlled by the growth duration. When the growth time is short, high density of QDs could be fabricated, but with a long growth time the small QDs get together to form a large cluster. We also show that with this growth method it is possible to grow both ZnSe quantum and ZnTe QDs on one substrate at the same time. For this dual QDs system, two peaks corresponding to the emission from the ZnSe dots (3.0 eV, blue–violet) and ZnTe dots (2.6 eV, green–blue) could be observed at the same time in the photoluminescence measurement.     

Study of Polycation-Capped Mn:ZnSe Quantum Dots as a Novel Fluorescent Probe for Living Cells

Transition metal manganese ion (Mn²⁺) doped zinc selenide quantum dots (Mn:ZnSe D-Dots) have been considered as a new material for fluorescent probes in biological labeling. However, this application is limited by the low membrane permeability of D-Dots. In this work, Mn:ZnSe D-Dots were capped with the polycation Sofast to label living cells. For the first time, the efficiency of cellular uptake in living cells is significantly enhanced. Various molar ratios of Sofast to D-Dots were explored and compared to obtain the optimal reaction conditions between Sofast and D-Dots for preparing Sofast/D-Dots nano-compound. A comparison on the fluorescence labeling ability of living cells were made between Sofast/D-Dots and pure D-Dots. Results from laser scanning confocal microscope show that Sofast/D-Dots complexes enter the cells more efficiently than pure D-Dots, even with a lower concentration and shorter incubation time. The cytotoxicities of D-Dots and Sofast/D-Dots were also studied. It was found that Sofast/D-Dots have a much lower cytotoxicity than cadmium-containing quantum dots (i.e. CdTe and CdTe/ZnS). Our results suggest that the non-heavy-metal-containing Sofast/D-Dots complexes have a great potential in the application of biological labeling, especially of long-time bioimaging in living cells.     

CdSe/ZnS量子点在倏逝波光纤pH传感中的应用

将新型量子点荧光传感技术与光纤倏逝波传感技术相结合,发展了一种基于量子点荧光效应并结合倏逝波传导进行溶液酸碱度检测的新型传感技术,具有灵敏度高、检测速度快、便于微环境检测、可实现远程探测、实时监测和原位分析等特点。详细介绍了用于倏逝波传感的锥柱组合型光纤荧光探头的制备方法,量子点在光纤探头表面的修饰流程,光谱与强度两种光纤pH传感平台的建立,并分别从响应范围、线性度、重复性和稳定性等方面对CdSe/ZnS量子点应用于光纤pH传感进行了评价。结果表明,在pH值为2~12的范围内,CdSe/ZnS量子点的荧光光谱信号的峰位在强酸和强碱的情况下都会产生红移,且红移量随pH值的变化呈线性关系,其量子点荧光强度信号随pH值的减小呈线性降低关系,通过在强酸和强碱下交替测试的实验表明其具有较好的重复性,利用荧光强度传感平台进行实时监测的实验表明其具有较好的稳定性。因此,将CdSe/ZnS量子点用于倏逝波光纤pH传感具有可行性,在生物化学、环境监测、医学临床、食品安全等领域的pH值测量方面有着广泛的应用前景。     

Temperature-dependent photoluminescence of dimethylzinc-treated ZnSe/ZnS quantum dots

Temperature-dependent photoluminescence (PL) measurements were carried out ZnSe/ZnS quantum dots (QDs) grown with post-growth interruption under a dimethylzinc (DMZn) flow. The PL spectra showed sigmoidal peak shifts and V-shaped full width at half maximum (FWHM) variations with increasing temperature, which strongly suggest that the QD structure of ZnSe/ZnS is quite similar to that of other material systems grown in the Stranski–Krastanov mode. Apparent differences are revealed as a consequence of DMZn treatment: (i) the PL spectra of ZnSe/ZnS QDs showed peaks at higher energies and persisted up to 300 K, and(ii) the minimum points of the V-shaped FWHM appear at a higher temperature compared to H₂-purged ZnSe/ZnS QDs. Experimental results demonstrate the enhancement of localization energy.     

Enhanced biocompatibility of ZnS:Mn quantum dots encapsulated with Aloe vera extract for therapeutic applications

Toxicity of nanoparticles remains to be a major issue in their application to the biomedical field. Aloe vera(AV) is one of the most widely exploited medicinal plants that have a multitude of amazing properties in the field of medicine.Methanol extract of Aloe vera can be used as a novel stabilising agent for quantum dots to reduce toxicity. We report the synthesis, structural characterization, antibacterial activity and cytotoxicity studies of ZnS:Mn quantum dots synthesized by the colloidal precipitation method, using methanol extract of Aloe vera(AVME) as the capping agent. The ZnS:Mn quantum dots capped with AVME exhibit superior performances in biocompatibility and antibacterial activity compared with ZnS:Mn quantum dots without encapsulation.     

Zn1—xMnx／ZnSe应变超晶格分子束外延生长及光学特性研究

用分子束外延方法在ＧａＡｓ（１００）衬底上成功生长了高质量的Ｚｎ１－ｘＭｎｘＳｅ／ＺｎＳｅ（ｘ＝０．１６），超晶格结构，用Ｘ射线衍射和低温光致发光（ＰＬ）对其结构，应变分布以及光学性能进行了研究，结果表明，２Ｋ温度下，Ｚｎ１－ｘＭｎｘＳｅ／ＺｎＳｅ超晶格的光致发光中主发光峰对应于ＺｎＳｅ阱中基态电子和基态轻空穴之间的自由激子跃迁，而且其峰位相对于ＺｎＳｅ薄膜材料的自由激子峰有明显移动。其中，当超晶