Re-charging the luminescence states in CdSe/ZnS quantum dots at the conjugation to Osteopontin antibodies

The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.     

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。     

Shell-dependent hole transport in highly luminescent CdSe-core CdS/ZnCdS/ZnS multi-shell nanocrystals

The photoinduced hole transfer dynamics from CdSe quantum dots (QDs), shelled with ZnS or CdS/CdZnS/ZnS layers, to organic hole transporting materials (HTMs) is investigated by absorption, steady-state and time-resolved photoluminescence (PL) spectroscopy. The PL intensity and lifetime of the QDs are dramatically quenched when HTMs are added into the dilute QD solution. The quenching efficiency of the QDs significantly decreases with increasing the shell thickness and increases with decreasing the oxidation potential of the HTMs. These facts are correlated with the photoinduced hole transfer from the QDs to the HTMs. The above results are helpful in understanding the photoexcitation dynamics-related phenomena of organic molecule conjugated nano-object.     

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。     

Temperature-dependent photoluminescence of CuInS2 quantum dots

Temperature-dependent photoluminescence (PL) spectroscopy of CuInS₂ core and CuInS₂/ZnS core–shell quantum dots (QDs) was studied for understanding the influence of a ZnS shell on the PL mechanism. The PL quantum yield and lifetime of CuInS₂ core QDs were significantly enhanced after the QD surface was coated with the ZnS shell. The temperature dependences of the PL energy, linewidth, and intensity for the core and core–shell QDs were studied in the temperature range from 92 to 287 K. The temperature-dependent shifts of 98 meV and 35 meV for the PL energies of the QDs were much larger than those of the excitons in their bulk semiconductors. It was surprisingly found that the core and core–shell QDs exhibited a similar temperature dependence of the PL intensity. The PL in the CuInS₂/ZnS core–shell QDs was suggested to originate from recombination of many kinds of defect-related emission centers in the interior of the cores.     

Experimental investigation of energy transfer between CdSe/ZnS quantum dots and different-sized gold nanoparticles

Hybrid nanostructures of quantum dots(QDs) and metallic nanostructure are attractive for future use in a variety of optoelectronic devices. For photodetection applications, it is important that the photoluminescence (PL) of QDs is quenched by the metallic nanostructures. Here, the quenching efficiency of CdSe/ZnS core-shell quantum dots (QDs) with different sized gold nanoparticles (NPs) films through energy transfer is investigated by measuring the PL intensity of the hybrid nanostructures. In our research, the gold NPs films are formed by the post-annealing of the deposited Au films on the quartz substrate. We find that the energy transfer from the QDs to the Au NPs strongly depends on the sizes of the Au NPs. For CdSe/ZnS QDs direct contact with the Au NPs films, the largest energy transfer efficiency are detected when the resonance absorption peak of the Au NPs is nearest to the emission peak of the CdSe/ZnS QDs. However, when there is a PMMA spacer between the QDs layer and the Au NPs films, firstly, we find that the energy transfer efficiency is weakened, and the largest energy transfer efficiency is obtained when the resonant absorption peak of the Au NPs is farthest to the emission peak wavelength of CdSe/ZnS QDs. These results will be useful for the potential design of the high efficiency QDs optoelectronic devices.     

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]。     

Steady State and Time Resolved Spectroscopic Study of CdSe and CdSe/ZnS QDs:FRET Approach

This article highlights some physical studies on the relaxation dynamics and Förster resonance energy transfer (FRET) of semiconductor quantum dots (QDs) to proximal dye molecule and the way these phenomena change with core to core-shell QD is discussed. Efforts to understand the optical and carrier relaxation dynamics of CdSe and CdSe/ZnS QDs are made by using absorption, steady-state fluorescence and time-resolved fluorescence (TCSPC) techniques. Steady-state as well as time-resolved fluorescence measurements were employed to evaluate the QD PL quenching induced by the proximal Rhodamine 101 dye molecule and to examine the influence of deep trap states on energy transfer efficiency. The FRET parameters such as spectral overlap, Förster distance, intermolecular distance for each donor-acceptor pair are determined and variation of these parameters from core to core-shell QD is discussed.     

2018年2期电子期刊

光诱导功能退化是胶体量子点在应用中面临的主要挑战之一,本文针对这一问题研究了使用磁控溅射沉积SiO₂薄膜形成钝化层来提高CdSe/ZnS量子点发光稳定性的方法。首先,通过三正辛基膦辅助连续离子层吸附反应方法合成了615 nm发光的红色CdSe/ZnS量子点。然后将量子点旋涂在SiO₂/Si基片上,再通过磁控溅射方法在量子点上沉积了厚度为20 nm的SiO₂薄膜作为钝化层。使用连续波激光光源分别在空气气氛和真空条件下照射样品,研究了经过不同照射时间后钝化和未钝化量子点的稳态光致发光光谱。结果表明,随着照射时间的延长,没有SiO₂钝化的量子点的PL强度显著降低、PL峰值发生蓝移、FWHM不断增大。对比研究发现,由于SiO₂薄膜能够阻挡空气中的水和氧,减缓了量子点表面的光诱导氧化现象,因此显著提高了CdSe/ZnS量子点的稳定性。     

Specific features of luminescence quenching in a nematic liquid crystal doped with nanoparticles

The change in the intensity of the photoluminescence (PL) spectra of nematic liquid crystal (NLC) composites as a function of the concentration of CdSe/ZnS semiconductor quantum dots (QDs) and TiO₂ and ZrO₂ nanoparticles ~5 nm in diameter has been investigated. It is shown that the PL-quenching intensity in composites with CdSe/ZnS QDs exceeds that in composites with TiO₂ and ZrO₂ nanoparticles. The lowfrequency spectra of these composites with a concentration of 0.1 wt %, recorded in the range of 10²–10³ Hz, and the content of mobile ions in them have been investigated. It is found that the dielectric loss in the composite with CdSe/ZnS QDs is much higher and the content of mobile ions is larger by a factor of 3 than in the composites with TiO₂ and ZrO₂ nanoparticles. It is shown that an increase in the CdSe/ZnS QD concentration in NLC composites leads to an increase in the dielectric loss and a decrease in the PL intensity. Possible mechanisms of the interaction between NLC molecules and CdSe/ZnS QDs are discussed.     

The influence of intrinsic and surface states on the emission properties of colloidal nanocrystals

Time Resolved Photoluminescence (TRPL) measurements on the picosecond time scale (temporal resolution of 17 ps) on colloidal CdSe and CdSe/ZnS Quantum Dots (QDs) were performed, to elucidate the role of intrinsic and surface states on the emission process. Transient PL spectra reveal three emission peaks with different lifetimes (60 ps, 460 ps and 9–10 ns, from the bluest to the reddest peak). The energy separations among the states, together with their characteristic decay times, allow us to attribute the two higher energy peaks to ±1^U and ±1^L bright states of the fine structure picture of spherical CdSe QDs, and the third one to surface states emission, respectively. We show that the contribution of surface emission to the PL results to be different for the two samples studied (67% in the CdSe QDs and 32% in CdSe/ZnS QDs), confirming the decisive role of the ZnS shell in the improvement of the surface passivation.     

Mercaptopropionic acid capped CdSe/ZnS quantum dots as fluorescence probe for lead(II)

MPA stabilized CdSe/ZnS NCs was applied as a fluorescent probe for the sensitive detection of Pb²⁺ in water. The microreaction was demonstrated as a facile method for the reproducible synthesis of CdSe/ZnS NCs with a high quantum yield. The good stability of CdSe/ZnS NCs was proved by the significant maintaining of photoluminescent (PL) after the ligand exchange with MPA, and was further demonstrated by the excellent PL property in water solution with various pH values. The cation exchange of Zn with Pb led to the linear quenching of PL with the concentration of Pb²⁺, which provided as an opportunity to apply MPA stabilized CdSe/ZnS NCs as fluorescent probes for Pb²⁺. A facile method by adjustment of QDs concentration was demonstrated as a suitable way to approach different detection limits. The detection limits of 0.03 and 3.3 μM were achieved by setting QDs solutions with the absorbance of the first exciton peak as 0.05 and 0.15, respectively.     

Photoluminescence Characteristics of ZnCuInS-ZnS Core-Shell Semiconductor Nanocrystals

The photoluminescence(PL) characteristics of ZnCuInS quantum dots(QDs) with varying ZnS shell thicknesses of 0, 0.5, and 1.5 layers are investigated systemically by time-correlated single-photon counting measurements and temperature-dependent PL measurements. The results show that a ZnS shell thickness of 1.5 layers can effectively improve the PL quantum yield in one order of magnitude by depressing the surface trapping states of the core ZnCuInS QDs at room temperature. However, the PL measurements at the elevated temperature reveal that the core-shell nanocrystals remain temperature-sensitive with respect to their relatively thin shells.The temperature sensitivity of these small-sized single-layered core-shell nanocrystals may find applications as effective thermometers for the in vivo detection of biological reactions within cells.     

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。     

Self-assembly of dandelion-like Fe3O4@C@BiOCl magnetic nanocomposites with excellent solar-driven photocatalytic properties

In comparison with conventional organic dyes, quantum dots (QDs) have unique optical and electronic properties, which provide QDs with a wide scope of prospective application in biology and biomedicine. However, the toxicity of QDs and the fluorescence intensity of labeled bacteria must precede their application in bacterial imaging and tracing in vivo. Here, we show that treatment with CaCl₂ significantly improved bacterial labeling efficiency of CdSe/ZnS QDs with the CdSe core size of ~3.1 nm (relative fluorescence unit (RFU) value and ratio of fluorescent E. coli) with rising CdSe/ZnS QDs concentration in a concentration-dependent manner. At 12.5 nmol/L CdSe/ZnS QDs concentration, labeled Escherichia coli (E. coli) DH5α appeared as short rod-shaped and luminescent with normal size, and the survival rate and ultrastructure did not change in comparison to the control. But the ratio of fluorescent bacteria and RFU were very low. However, the survival rate of transformed E. coli was significantly inhibited by high CdSe/ZnS QDs concentrations (≥25 nmol/L). Moreover, internalization of CdSe/ZnS QDs resulted in ultrastructure damage of transformed E. coli in a concentration-dependent manner (≥25 nmol/L). Therefore, CdSe/ZnS QDs may not suitable for tracing of bacteria in vivo. Moreover, our study also revealed that colony-forming capability assay and transmission electron microscopy could be used to comprehensively evaluate the toxicity of QDs on labeled bacteria. Our findings do provide a new direction toward the improvement and modification of QDs for use in imaging and tracing studies in vivo.     

ZnS薄膜参数对有机/无机复合发光器件特性的影响

半导体量子点(QDs)具有发光效率高和发光波长可调等特点。采用胶体CdSe QDs作电致发光器件的有源材料,TPD(N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine)作空穴传输层,ZnS作电子传输层,研究了有机/无机复合发光器件ITO/TPD/CdSe QDs/ZnS/Ag的电致发光特性。TPD和CdSe QDs薄膜采用旋涂方法、ZnS薄膜采用磁控溅射方法沉积,器件表面平整。CdSe QDs的光致发光和电致发光谱峰位波长均位于～580 nm,属于量子点的带边激子发光。我们与以前的ITO/ZnS/CdSe QDs/ZnS/Ag发光器件结构进行了对比,发现新的器件结构的电致发光谱没有观察到QDs表面态的发光,而且新器件的发光强度是ITO/ZnS/CdSe QDs/ZnS/Ag结构的～10倍。发光效率的提高归因于碰撞激发与载流子注入两种发光机制并存的结果：一方面电子经过ZnS 层加速后,碰撞激发CdSe QDs发光;另一方面,空穴从TPD层注入CdSe QDs 与QDs中激发的电子复合发光。我们进一步研究了ZnS电子加速层厚度对发光特性的影响,选择ZnS薄膜的厚度分别是80,120 和160 nm,发现随着ZnS层厚度增大,器件启亮电压升高,EL强度增大,但是击穿电压降低。EL峰位随着ZnS厚度的减小发生明显蓝移,对上述实验现象进行了机理解释。     

Photoluminescence of colloidal CdSe nano-tetrapods and quantum dots in oxygenic and oxygen-free environments

The effects of oxygenic versus oxygen-free environments on colloidal CdSe nano-tetrapods and quantum dots (QDs) were studied using both continuous and time-resolved photoluminescence (PL) measurements. The decays of PL intensities for tetrapods and QDs in oxygen-free solution (chloroform) and in air (on silicon) can be well fitted by a bi-exponential function. Based on the emission-energy dependence of carrier lifetimes and the amplitude ratio of the fast-decay component to the slow-decay component, the fast and slow PL decays of CdSe nanocrystals are attributed to the recombination of delocalized carriers in the core states and localized carriers in the surface states, respectively. The PL intensities of CdSe nano-tetrapods and QDs were found to be five times and an order of magnitude higher in air than in vacuum, respectively, which is explained by the passivation of surface defects by the polar gas (oxygen) absorption. The lower enhancement in PL intensities of CdSe nano-tetrapods is explained by the special morphology of the tetrapods.     

生物偶联过程对于聚合物包覆的水溶性CdSe/ZnS核壳量子点发光的影响

以传统的戊二醛交联的方法实现了聚丙烯酸包覆的CdSe/ZnS量子点和人IgG蛋白分子的偶联,同时研究了偶联过程对量子点发光性能的影响。通过琼脂糖凝胶电泳技术证明量子点和蛋白分子偶联成功。通过稳态光谱和时间分辨光谱研究了偶联过程对量子点荧光性质的影响。发现偶联到量子点表面的戊二醛分子能够破坏量子点的表面从而增加其表面缺陷,使量子点发光效率降低;上述产物进一步与人IgG偶联增强了量子点的荧光强度,这是由于连接到量子点上的蛋白分子修复了量子点的表面,从而降低了表面缺陷所致。     

单核/双壳结构CdSe/CdS/ZnS纳米晶的合成与发光性质

以巯基乙酸为稳定剂,在水溶液中合成了单核/双壳结构的CdSe/CdS/ZnS纳米晶。在内核CdSe和外壳ZnS之间的内壳CdS作为晶格匹配调节层,能够很好的改善核/壳界面处的性能,而且,最外层ZnS能够最大程度地使激子受限。用TEM和XPS对纳米晶进行了表征,并且用光致发光光谱和吸收光谱对不同核壳结构的纳米晶的发光性能进行了比较,结果表明单核/双壳结构的纳米晶具有更加优异的发光特性。     

Reflective photoluminescence fiber temperature probe based on the CdSe/ZnS quantum dot thin film

A reflective fiber temperature sensor based on the optical temperature dependent characteristics of a quantum dots (QDs) thin film is developed by depositing the CdSe/ZnS core/shell quantum dots on the SiO₂ glass substrates. As the temperature is changed from 30 to 200°C, the peak wavelengths of PL spectra from the sensing head increase linearly with the temperature, while the peak intensity and the full width at half maximum (FWHM) of PL spectra vary exponentially according to the specific physical law. Using the obtained temperature-dependent peak-wavelength shift, the average resolution of the designed fiber temperature sensor can reach 0.12 nm/°C, while it reaches 0.056 nm/°C according to the FWHM of PL spectrum.