Enhanced chemiluminescence from reactions between CdTe/CdS/ZnS quantum dots and periodate

A novel chemiluminescence (CL) performance of CdTe/CdS/ZnS quantum dots (QDs) with periodate (KIO₄) was studied. Effects of concentration and pH on the CL system were investigated. Electron spin resonance (ESR) and the effects of radical scavenger analysis were employed for identification of intermediate species. The CL spectra for this system showed only one maximum emission peak centered around 620 nm, which was similar with photoluminescence (PL) spectra of CdTe/CdS/ZnS QDs. The CL of CdTe/CdS/ZnS QDs was induced by direct chemical oxidation and the possible mechanism could be explained by radiative recombination of injected holes and electrons. This investigation not only provided new sight into the optical characteristics of CdTe/CdS/ZnS QDs, but also broadened their potential optical utilizations.     

Aqueous synthesis of glutathione-capped CdTe/CdS/ZnS and CdTe/CdSe/ZnS core/shell/shell nanocrystal heterostructures

Here we demonstrate the aqueous synthesis of colloidal nanocrystal heterostructures consisting of the CdTe core encapsulated by CdS/ZnS or CdSe/ZnS shells using glutathione (GSH), a tripeptide, as the capping ligand. The inner CdTe/CdS and CdTe/CdSe heterostructures have type-I, quasi-type-II, or type-II band offsets depending on the core size and shell thickness, and the outer CdS/ZnS and CdSe/ZnS structures have type-I band offsets. The emission maxima of the assembled heterostructures were found to be dependent on the CdTe core size, with a wider range of spectral tunability observed for the smaller cores. Because of encapsulation effects, the formation of successive shells resulted in a considerable increase in the photoluminescence quantum yield; however, identifying optimal shell thicknesses was required to achieve the maximum quantum yield. Photoluminescence lifetime measurements revealed that the decrease in the quantum yield of thick-shell nanocrystals was caused by a substantial decrease in the radiative rate constant. By tuning the diameter of the core and the thickness of each shell, a broad range of high quantum yield (up to 45%) nanocrystal heterostructures with emission ranging from visible to NIR wavelengths (500-730 nm) were obtained. This versatile route to engineering the optical properties of nanocrystal heterostructures will provide new opportunities for applications in bioimaging and biolabeling.     

CdTe/CdS量子点的Ⅰ-Ⅱ型结构转变与荧光性质

制备了壳层厚度可以精确控制的CdTe/CdS核壳量子点, 利用紫外-可见吸收光谱、光致发光光谱、透射电镜和时间分辨光谱等技术, 分析了CdS壳层厚度对CdTe量子点的荧光量子产率和光谱结构的影响规律. 发现了不同于CdSe/CdS, CdSe/ZnS, CdTe/ZnS等核壳量子点的荧光峰展宽、大幅度红移以及荧光寿命大幅度增加现象. 根据能带的位置关系, 随着CdS厚度的增加, CdTe从Ⅰ型结构逐渐过渡到Ⅱ型核壳结构. 对于Ⅱ型CdTe/CdS核壳量子点, 不仅存在CdTe核区导带电子与价带空穴间的直接复合, 还存在CdS壳层导带电子与CdTe核价带空穴界面处的间接复合, 发光机制的变化导致荧光峰的展宽、明显红移和荧光寿命的增加. 当壳层过厚时, 壳层表面新引入的缺陷会阻碍荧光寿命和量子产率的进一步提高.     

水溶性的高荧光CdTe/CdSeⅡ型核壳量子点的合成与表征

用L-半胱氨酸(L-cysteine)作为稳定剂,以制备的CdTe量子点为核模板,水相合成了具有近红外发光的Ⅱ型核壳CdTe/CdSe半导体量子点。实验考察了合成温度,核模板的尺寸和组分比等因素对合成高质量的CdTe/CdSe量子点的影响。用紫外-可见吸收和荧光光谱研究了合成的量子点的光学性质。在优化的合成条件下,荧光发射光谱在586～753nm范围连续可调,荧光量子产率高达68%;通过X-射线衍射(XRD),X射线光电子能谱(XPS)和透射电镜(TEM)对合成的Ⅱ型核壳CdTe/CdSe量子点进行了结构和形貌表征。     

Silica Coating of Water-Soluble CdTe/CdS Core-Shell Nanocrystals by Microemulsion Method

"Using Te powder as a tellurium source and Na2S as a sulfur source, core-shell CdTe/CdS NPs were synthesized at 50 oC. UV-visible and photoluminescence (PL) spectra were used to probe the effect of CdS passivation on the CdTe quantum dots. As the thickness of CdS shell increases, there is a red-shift in the optical absorption spectra, as well as the PL spectra. The broadening absorption peaks and PL spectra indicate that the size distributions of CdTe/CdS NPs widen increasingly with the increase of CdS coverage. The PL spectra also show that the fluorescence intensity of CdTe QDs will increase when the particles are covered with CdS shell with ratio of S/Te less than 1.0, otherwise it will decrease if the ratio of S/Te is larger than 1.0. Furthermore, the (CdTe/CdS)@SiO2 particles were prepared using a water-in-oil microemulsion method at room temperature in which hydrolysis of tetraethyl orthosilicate leads to the formation of monodispersed silica nanospheres. The obtained (CdTe/CdS)@SiO2 particles show bright photoluminescence with their fluorescence intensity being enhanced 18.5% compared with that of CdTe NPs. TEM imaging shows that the diameter of these composite particles is 50 nm. These nanoparticles are suitable for biomarker applications since they are much smaller than cellular dimensions."     

One-pot synthesis of CuInS2 and CuInS2/MS (M=Cd,Zn) core–shell luminescent nanocrystals: a low-temperature and low-cost approach

The single-pot synthesis of highly crystalline and fluorescent chalcopyrite CuInS₂ (CIS) colloidal nanoparticles has been reported by thermal decomposition of metal ethyl xanthate (at ~110 °C) for the first time. The fluorescence emission wavelength can also be readily tuned from the UV to the visible region by merely prolonging the reaction time, as the PL emission may be varied from 550 to 675 nm. The synthesized CIS is subjected to postdeposition treatment with CdS/ZnS in one pot route using cadmium/zinc xanthate at low temperature (~80 °C) to improve the quantum yield of core–shell (CIS/CdS or ZnS) nanocrystallites as compared to CIS core. The stability of core–shell particularly CIS/ZnS system upon continuous laser exposure suggests the formation of surface bonds with superior mechanical stability. This low-cost synthesis of such nontoxic QDs using green chemical routes is a promising approach for the fabrication of optoelectronic and biosensing devices. Graphical Abstract

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CdTe/CdS核壳量子点与蛋白质荧光标记

利用连续离子层吸附技术合成了水溶性的CdTe／CdS核壳量子点．通过CdS壳层的包覆,量子点的量子效率由原来的15％（裸核）提高到38％（核壳）,这种核壳结构量子点的化学和光学性质具有更好的稳定性,可以用于生物标记．本文采取共价连接与静电吸附两种方法,实现了量子点的生物标记,电泳技术已证明,应用这种量子点成功地实现了对蛋白质分子的生物标记．通过对量子点与蛋白质偶联前后的荧光光谱分析,发现量子点与蛋白质作用后荧光增强是由于蛋白质对量子点进行了表面修饰,从而降低了表面缺陷引起的非辐射跃迁几率所致．通过共价连接量子点的荧光峰位红移,主要是由于偶极-偶极相互作用引起的;量子点与蛋白质静电吸附作用引起的荧光峰位蓝移主要起因于量子点表面电荷量的降低．     

水热法合成AgInS2/ZnS核/壳结构量子点及其荧光性能

以硫脲为硫源,采用谷胱甘肽(GSH)和柠檬酸钠(SC)为配体,通过水热法制备了水溶性AgInS2/ZnS(AIS/ZnS)核/壳结构量子点。系统研究了反应温度和配体用量对量子点的合成及其荧光性能的影响。采用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)和光致发光光谱(PL)分别对量子点的物相、形貌和光学性能进行了表征,并考察了量子点的稳定性。实验结果表明,随着反应温度从70℃升高至90℃,促进了ZnS壳层的形成,有效地钝化了量子点的表面缺陷,获得的AIS/ZnS核/壳量子点的发光强度显著提高,发光峰位从600 nm蓝移至580 nm。配体的添加可以有效地平衡Zn^2+的化学反应活性,减缓ZnS壳层的生长,抑制核壳界面缺陷的形成,还能消除量子点的表面态,当nGSH/nZn^2+=2.0,nSC/nZn^2+=2.5时,AIS/ZnS量子点的荧光性能最佳。此外,AIS/ZnS核/壳结构量子点还具有优异的光学稳定性。     

水溶性的CdSe/CdS/ZnS量子点的合成及表征

用L-半胱氨酸盐(Cys)作为稳定剂,合成了水溶性的双壳结构的CdSe/CdS/ZnS半导体量子点。吸收光谱和荧光光谱结果表明,双壳结构的CdSe/CdS/ZnS纳米微粒比单一的CdSe核纳米粒子和单核壳结构的CdSe/CdS纳米粒子具有更优异的发光特性。用透射电子显微镜(TEM)、ED、XRD、XPS和FTIR等方法对CdSe核和双壳层的CdSe/CdS/ZnS纳米微粒的结构、分散性及形貌分别进行了表征。     

Luminescence of Polyethylene Glycol Coated CdSeTe/ZnS and InP/ZnS Nanoparticles in the Presence of Copper Cations

The use of click chemistry for quantum dot (QD) functionalization could be very promising for the development of bioconjugates dedicated to in vivo applications. Alkyne–azide ligation usually requires copper(I) catalysis. The luminescence response of CdSeTe/ZnS nanoparticles coated with polyethylene glycol (PEG) is studied in the presence of copper cations, and compared to that of InP/ZnS QDs coated with mercaptoundecanoic acid (MUA). The quenching mechanisms appear different. Luminescence quenching occurs without any wavelength shift in the absorption and emission spectra for the CdSeTe/ZnS/PEG nanocrystals. In this case, the presence of copper in the ZnS shell is evidenced by energy‐filtered transmission electron microscopy (EF‐TEM). By contrast, in the case of InP/ZnS/MUA nanocrystals, a redshift of the excitation and emission spectra, accompanied by an increase in absorbance and a decrease in photoluminescence, is observed. For CdSeTe/ZnS/PEG nanocrystals, PL quenching is enhanced for QDs with 1) smaller inorganic‐core diameter, 2) thinner PEG shell, and 3) hydroxyl terminal groups. Whereas copper‐induced PL quenching can be interesting for the design of sensitive cation sensors, copper‐free click reactions should be used for the efficient functionalization of nanocrystals dedicated to bioapplications, in order to achieve highly luminescent QD bioconjugates.     

油溶性CuInS2/ZnS量子点的制备及其温敏性聚丙烯酰胺胶束介导的水相转移

采用非热注法成功制备了高质量的油溶性CuInS2/ZnS核壳量子点,量子点的荧光发射峰在可见光到近红外范围内可调(550～800 nm),且荧光量子产率最高达80%。本文进一步利用具有温敏特性的聚丙烯酰胺胶束作相转移剂,成功地将油溶性的CuInS2/ZnS核壳量子点转移入水相。水相中自组装形成的CuInS2/ZnS量子点-胶束复合物不仅具有良好的荧光性质,而且胶束原有的灵敏的热响应性被保留。这些研究初步表明,无镉的低毒的CuInS2/ZnS量子点可作为纳米胶束的荧光示踪探针。     

油溶性CuInS2/ZnS量子点的制备及其温敏性聚丙烯酰胺胶束介导的水相转移

采用非热注法成功制备了高质量的油溶性CuInS₂/ZnS核壳量子点, 量子点的荧光发射峰在可见光到近红外范围内可调(550~800 nm), 且荧光量子产率最高达80%。本文进一步利用具有温敏特性的聚丙烯酰胺胶束作相转移剂, 成功地将油溶性的CuInS₂/ZnS核壳量子点转移入水相。水相中自组装形成的CuInS₂/ZnS量子点-胶束复合物不仅具有良好的荧光性质, 而且胶束原有的灵敏的热响应性被保留。这些研究初步表明, 无镉的低毒的CuInS₂/ZnS量子点可作为纳米胶束的荧光示踪探针。     

Ultrafast synthesis of near-infrared-emitting aqueous CdTe/CdS quantum dots with high fluorescence

The traditional aqueous route to synthesis CdTe/CdS Core/shell (c/s) quantum dots (QDs) via decomposition of Cd-thiol complexes is usually time consuming. Herein, an ultrafast and facile aqueous synthetic approach under atmospheric pressure for CdTe/CdS c/s QDs with emission from the green to the near-infrared window (535–820 nm) is reported. With purified CdTe core QDs diluted in solution of Cd-3-mercaptopropionic acid (MPA) complexes, CdTe/CdS c/s QDs with emission wavelengths at 700 and 800 nm can be obtained within 20- and 45-min refluxing under the optimized experimental conditions, respectively. This is the most rapid way to prepare CdTe/CdS c/s QDs in aqueous phase, and the obtained QDs were highly luminescent without postsynthesis treatment. The influences of various experimental factors, including Cd²⁺ concentration, MPA-to-Cd ratio, pH value, and dilution ratio on the growth rate and luminescent properties of the obtained CdTe/CdS c/s QDs, have been taken into consideration. The three processes “purification-dilution-addition” ensure the synthesis environment with high pH value and low core concentration and have a marked impact on the rapid synthesis rate and the resulting high fluorescence of CdTe/CdS c/s QDs.     

Single-source precursor route for overcoating CdS and ZnS shells around CdSe core nanocrystals

We reported a facile route for overcoating CdS and ZnS shells around colloidal CdSe core nanocrystals. To synthesize such double shelled core/shell nanocrystals, first, CdSe core nanocrystals were prepared in a much “greener” and cheap route, which did not involve the use of hazardous and expensive trioctylphosphine. Then, a low-cost and labor-saving route was adopted for the CdS and ZnS shell growth with the use of thermal decomposition of commercial available air stable single-source precursors cadmium diethyldithio-carbamate and zinc diethyldithiocarbamate in a non-coordinating solvent at intermediate temperatures. Powder X-ray diffraction patterns and transmission electron microscopy images confirm the epitaxial growth of the shell in the core/shell nanocrystals. The photoluminescence quantum yield of the resulting CdSe/CdS/ZnS core/shell nanocrystals can be as high as 90% in organic media and up to 60% after phase transfer into aqueous media. By varying the size of CdSe cores, the emission wavelength of the obtained core/shell nanostructures can span from 554 to 636 nm.     

一锅合成绿色到近红外发射的CdTe量子点

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法制备了从绿色到近红外发射的CdTe量子点。系统研究了反应液pH值、镉和碲的物质的量之比及镉和3-巯基丙酸的物质的量之比等实验条件对CdTe量子点体系的发射波长和荧光量子产率的影响。在pH值为10.5,且nCd2+∶nTe2-∶nMPA=1∶0.05∶1.1的条件下,回流0.5 h,CdTe量子点体系在569 nm波长处的荧光量子产率达到30.8%;在7 h的回流时间内,制备的量子点的波长覆盖范围为525～730 nm。分别用X射线粉末衍射、透射电镜和红外光谱对CdTe量子点的晶体结构、形貌及表面基团进行表征。     

PAMAM树形分子模板法原位制备CdS-ZnS核-壳结构量子点

以4、5代PAMAM树形分子(64个酯端基)为模板, 在树形分子空腔内原位合成了CdS-ZnS核-壳结构量子点, 并对其形貌和光学性能进行了表征. HRTEM观察发现量子点分散良好, 尺寸均匀, 平均粒径约为2.3 nm. UV-Vis光谱证明ZnS外延生长在CdS核外, EDS能谱也证明了核壳结构的生成. 适当厚度的ZnS壳层可使光致发光效率提高至31%. PAMAM树形分子包在CdS-ZnS核-壳结构量子点外, 构成一层有机壳, 有效地限制了粒子聚集, 钝化了CdS量子点表面, 提高了发光效率. 另外， PAMAM树形分子良好的溶解性也赋予了量子点在不同极性溶剂中良好的溶解性, 提高了其稳定性.     

CdSe包覆层数对水溶性CdTe/CdSe (II型)核壳量子点的光学特性和微观结构的影响

在水相合成的CdTe量子点的体系中通过分批次加入新鲜配制的NaHSe和CdCl2溶液,制备出了CdSe包覆层数不同的CdTe/CdSe核壳量子点,并着重考察了CdSe包覆层数对CdTe/CdSe核壳量子点的光学特性以及微观结构的影响.与CdTe量子点相比,CdSe单层包覆的CdTe/CdSe核壳量子点的吸收峰和荧光发射峰出现明显红移;随着CdSe包覆层数的增多,CdTe/CdSe核壳量子点吸收光谱的覆盖范围向长波方向扩展,荧光发射峰强度逐步下降,荧光寿命大幅延长,体现出Ⅱ型核壳量子点的特征.X射线衍射(XRD)分析表明,随着CdSe包覆层数的增多,CdTe/CdSe核壳量子点的粉末衍射峰由CdTe衍射峰位置逐步向CdSe衍射峰位置靠近.CdTe/CdSe核壳量子点因其延伸到近红外区域的宽吸收特性致使其在太阳电池领域具有重要的应用前景.     

核壳结构CdS/ZnS纳米微粒的制备与光学特性

CdS and CdS/ZnS core-shell structure nano particles were synthesized in micro emulsion, and characterized by X-ray diffraction(XRD), transmission electron microscopy (TEM), UV absorption spectra and PL. The average diameter of CdS was about 3.3 nm, and CdS/ZnS core-shell structure was confirmed by XRD and UV. Considering the optical properties of CdS/ZnS core-shell structure nanoparticles which have different ZnS shell thickness, the UV absorption edge of CdS/ZnS becomes as lightred-shift with the thickness of ZnS layer increasing, and the absorption of shortwave band is strongly enhanced at the same time. The PL spectra indicate that ZnS shell layer can greatly eliminate surface defects of CdS nanoparticles and make its band-edge directed recombination increased, and the luminous efficiency of CdS is improved greatly when it has appropriate shell thickness.     

Modification of CdTe quantum dots as temperature-insensitive bioprobes

CdTe quantum dots (QDs) were synthesized in aqueous solution with 3-mercaptopropionic acid (MPA) as the stabilizer. The photoluminescence (PL) of CdTe QDs (3.5nm) is found to be temperature-dependent: as the temperature arising from 278K to 323K, the PL intensity declines to 50.2% of its original and PL emission peak shows obvious red-shift ( approximately 7nm). After modification of the QDs surface with denatured ovalbumin, the PL is more temperature-insensitive than before. The PL intensity retains more than 70% of its original and the emission peak shows less red-shift ( approximately 2nm). Moreover, it is found that the PL intensity and wavelength of denatured ovalbumin coated CdTe QDs are reversible during heating (323K)-cooling (278K) cycles. All the studies provide an important theoretical basis for searching temperature-insensitive bioprobes.     

Versatile Tri(pyrazolyl)phosphanes as Phosphorus Precursors for the Synthesis of Highly Emitting InP/ZnS Quantum Dots

Tri(pyrazolyl)phosphanes ( 5 ^R1,R2) are utilized as an alternative, cheap and low‐toxic phosphorus source for the convenient synthesis of InP/ZnS quantum dots (QDs). From these precursors, remarkably long‐term stable stock solutions (>6 months) of P(OLA)₃ (OLAH=oleylamine) are generated from which the respective pyrazoles are conveniently recovered. P(OLA)₃ acts simultaneously as phosphorus source and reducing agent in the synthesis of highly emitting InP/ZnS core/shell QDs. These QDs are characterized by a spectral range between 530–620 nm and photoluminescence quantum yields (PL QYs) between 51–62 %. A proof‐of‐concept white light‐emitting diode (LED) applying the InP/ZnS QDs as a color‐conversion layer was built to demonstrate their applicability and processibility.