CdSe与CdSe/ZnS核壳型量子点的制备方法与展望

CdSe及CdSe/ZnS量子点具有特殊的发光性质性质,它们在生物荧光探针、生物芯片、激光器、光电子器件和光催化等领域具有广泛的应用,现在越来越多的研究者更加关注它们在生命科学研究中起到得定性和定量标识生物分子和细胞作用。本文对几种制备CdSe及CdSe/ZnS量子点的方法进行了简单的综述,分别介绍了CdSe的水相、有机相以及绿色合成法,CdSe/ZnS量子点的热注入有机金属法和水相合成法,对这几种方法的优缺点进行了概述,并对其前景做了展望。     

CdSe:Mn量子点的制备及其光致发光特性研究

采用低温水热法,以柠檬酸为配位稳定剂制备了Mn2 掺杂的CdSe量子点.用紫外吸收光谱、荧光发射光谱、X射线衍射(XRD)、透射电镜(TEM)等进行了表征.研究了Mn2 掺杂浓度对量子点的结构及其光致发光性能的影响.光致发光光谱表明,当粒子尺寸为3 nm时,在580 nm处出现了属于Mn2 的4T1-6A1跃迁的特征发射峰.当激发波长为480nm时,在630nm处出现了CdSe的表面缺陷发射峰.随着Mn2 的掺杂浓度增大,CdSe:Mn表面陷阱态发射峰位置没有显著红移.TEM分析结果显示,CdSe:Mn量子点为单分散的,尺寸约为5 nm的圆形纳米粒子.当Mn2 离子掺杂浓度不大于5%时,Mn2 取代表面晶格中的Cd2 离子位置形成辐射性表面缺陷,产生表面陷阱态发射.吸收光谱显示,随着量子点变小,吸收带边发生蓝移,显示明显的量子尺寸效应.     

CdSe量子点与对氨基苯磺酸偶联反应研究

以巯基丙酸为修饰剂合成水溶性硒化镉量子点(CdSe/MPA),利用碳化二亚胺(EDC)和琥珀酰亚胺(NHS)两种偶联剂,将对氨基苯磺酸与硒化镉量子点进行偶联以制备量子点-对氨基苯磺酸偶合物.通过透射电子显微镜、紫外-可见光谱、荧光光谱、荧光寿命、红外光谱、毛细管电泳对偶合物进行了表征.结果表明:量子点和对氨基苯磺酸偶联...     

CdSe∶Mn量子点的制备及其光致发光特性研究

采用低温水热法,以柠檬酸为配位稳定剂制备了Mn2＋掺杂的CdSe量子点。用紫外吸收光谱、荧光发射光谱、X射线衍射（XRD）、透射电镜（TEM）等进行了表征。研究了Mn2＋掺杂浓度对量子点的结构及其光致发光性能的影响。光致发光光谱表明,当粒子尺寸为3 nm时,在580 nm处出现了属于Mn2＋的4T1-6A1跃迁的特征发射峰。当激发波长为480 nm时,在630 nm处出现了CdSe的表面缺陷发射峰。随着Mn2＋的掺杂浓度增大,CdSe∶Mn表面陷阱态发射峰位置没有显著红移。TEM分析结果显示,CdSe∶Mn量子点为单分散的,尺寸约为5 nm的圆形纳米粒子。当Mn2＋离子掺杂浓度不大于5%时,Mn2＋取代表面晶格中的Cd2＋离子位置形成辐射性表面缺陷,产生表面陷阱态发射。吸收光谱显示,随着量子点变小,吸收带边发生蓝移,显示明显的量子尺寸效应。     

用环己烷-水两相体系优化合成CdSe量子点

采用环己烷和水组成的两相体系,合成了不同粒径大小的硒化镉量子点。用X射线粉末衍射仪（XRD）,透射电子显微镜（TEM）,荧光光谱仪和紫外可见分光光度计等测试手段对产物进行了表征,结果表明生成的量子点粒径尺寸分布均匀,为立方晶型,具有良好的荧光特性。讨论了反应物比例、反应温度、反应时间、硒单体的量等因素对CdSe量子点的粒径分布,表面缺陷,奥斯德瓦尔效应的影响。通过优化实验条件,得到了表面缺陷少,粒径分布均匀,光量子效率高的硒化镉量子点。     

生物质基碳量子点的制备及其光谱性质研究

以木屑为前驱物制备的活性炭为碳源,采用化学氧化法,用聚乙二醇2000进行表面钝化,制备出了水溶性的生物质基碳量子点。优化了CQDs的合成方法：0.3 g生物质基活性炭, 40 mL HAc-80 mL 30% H₂O₂ 混合氧化剂,反应温度为100 ℃,反应时间为12 h。采用微波和超声结合法进行钝化,修复了CQDs的表面缺陷,荧光强度和量子产率均得到了提高。采用透射电子显微镜、紫外-可见吸收光谱仪、荧光分光光度计和傅里叶红外分光光度计进行表征,所合成的碳量子点发光性能优异、粒径小、分散性好,且无团聚现象。进一步考察了光照、温度和体系pH值对碳量子点性能的影响,结果表明,光稳定性好,抗光漂白性优异,荧光强度具有pH值依赖性,且易于表面功能化。     

PAMAM树状大分子模板法合成CdSe量子点及其发光性质的研究

以聚酰胺-胺(PAMAM)树状大分子为模板合成了CdSe量子点,X-射线粉末衍射(XRD)分析表明产品与闪锌矿结构的CdSe晶体的标准粉末衍射花样的3个强峰位置相同,透射电镜(TEM)分析显示CdSe量子点包裹在树状大分子孔隙中,分散良好.实验表明以2.5 G和3.5 G PAMAM为模板合成的产品没有检测到荧光发射,而以4.5 G PAMAM树状大分子为模板制备的产品在410～465 nm范围内有较强的荧光发射,其发光波长随反应温度改变.     

11-巯基烷酸修饰的核/壳量子点CdSe/ZnS的合成及分析应用研究

以11-巯基烷酸作为修饰剂,在水相中合成了CdSe/ZnS量子点荧光探针(QDs),并将其用于测定牛血清白蛋白.从透射电子显微镜看到该量子点外观近似球形,粒径约为15 nm.该核/壳量子点紫外吸收峰为460 nm,荧光发射峰为548nm,其荧光强度比单核量子点增强2.1倍.而且在至少40 d里,荧光强度基本保持稳定.在最佳条件下,实验表明了CdSe/ZnS QDs-BSA体系的荧光强度与BSA浓度呈线性关系,线性响应范围为10.0～50.0 mg/L,线性方程为△F=141.29 1.259c(c:mg/L),r=0.999 1.该方法应用于合成样品的测定中得到满意的结果.     

CdSe量子点的合成及其对潜指纹的荧光显现研究

以水热法在水相中直接合成了巯基乙酸修饰的CdSe量子点,并将合成的CdSe量子点进行表征、纯化。在波长365nm紫外光的激发下,CdSe量子点发射出明亮的黄绿色荧光,荧光发射峰约位于528nm,将得到的CdSe量子点纳米发光材料应用于非渗透性客体上潜指纹的荧光标记成像研究,发现CdSe量子点溶液显现的手印纹线流畅,显现细节特征明显,呈现明亮的黄绿色荧光指纹,具有很高的实用价值和鉴定价值。     

核壳式CdSe/ZnS量子点对邻苯二甲酸二丁酯的快速高灵敏荧光测定

用水热反应法制备了核壳式CdSe/ZnS量子点并用透射电镜进行形貌表征,将该量子点作为荧光探针,基于邻苯二甲酸二丁酯(DBP)的荧光增强效应,建立了一种快速测定DBP的方法。在最优条件(pH7.0,反应时间15 min,水作溶剂)下,DBP对CdSe/ZnS量子点的荧光增强作用最显著,在1.0～20.0μg/L范围内荧光信号强度与DBP浓度的对数呈线性关系,检出限为0.21μg/L,相关系数R²为0.99。该方法可用于白酒中DBP的含量测定,与现有标准方法GC-MS比较,具有高的检测灵敏度和准确性。     

谷氨酰胺为稳定剂制备硒化镉纳米晶及光谱性质研究

以谷氨酰胺(Gln)为稳定剂合成了硒化镉纳米晶,利用X-射线粉末衍射(XRD)和透射电镜(TEM)对纳米晶结构进行了表征,粒径约为20 nm。通过紫外-可见吸收光谱、激发光谱与发射光谱研究了纳米晶光谱特性。实验结果表明,反应温度过高、反应时间过长都会破坏谷氨酰胺(Gln)的稳定作用,使CdSe聚集,影响其荧光性质。而聚乙二醇(PEG)的加入会使纳米晶的荧光发射明显加强,而且发射峰峰形尖锐。     

Electrospinning of fluorescent fibers from CdSe/ZnS quantum dots in cellulose triacetate

Fluorescent cellulose triacetate (CTA) fibers were prepared by electrospinning solutions of CTA dissolved in an 8 : 2 v/v cosolvent system of methylene chloride (MC) and methanol (MeOH) which contained CdSe/ZnS quantum dots (QDs). The relatively low loading of colloidal nanoparticles was sufficient to impart fluorescence to the fibers but did not significantly alter fiber morphologies, which tended toward smooth surfaces with the occasional longitudinal feature. The fibers were birefringent due to the alignment of the polymer chains which occurred during electrospinning and had widths on the order of a hundred nanometers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Understanding the atomic and electronic structures origin of defect luminescence of CdSe quantum dots in glass matrix

Well-defined density functional theory (DFT) calculations are performed as the first exploratory study for the atomic and electronic mechanism of defect mediated morphology and optical properties of Cd_nSe_n (n = 3, 10, 13, and 33) quantum dots (QDs) in inorganic amorphous matrix. The intrinsic defects of pristine CdSe QDs, and the interfacial defects between the QDs and surrounding amorphous matrix, were systematically studied. The calculated electronic structure suggested that the pristine CdSe QDs capped by the structural modifiers or non-bridging oxygen in the amorphous matrix gave rise to the structure reconstruction and paired defect states at the edge of the valence and conduction bands. The orbital analysis elucidated that the redistribution of the majority of HOMO and LUMO electron density was localized over the bonds formed by capping atoms and QDs. These changes in the electronic structures were further demonstrated by CdSe QDs embedded sodium silicate glasses. It turned out that Se atoms at QDs/glass interface were much more active than those found on the surface of organically passivated CdSe QDs. The results serve as a new paradigm in materials research to explore structural origins of defect emission from QDs and a new strategy to develop glasses containing QDs with high photoluminescence quantum efficiency.     

Time-dependent pH sensing phenomena using CdSe/ZnS quantum dots in EIS structure

Time-dependent pH sensing phenomena of the core-shell CdSe/ZnS quantum dot (QD) sensors in EIS (electrolyte insulator semiconductor) structure have been investigated for the first time. The quantum dots are immobilized by chaperonin GroEL protein, which are observed by both atomic force microscope and scanning electron microscope. The diameter of one QD is approximately 6.5 nm. The QDs are not oxidized over a long time and core-shell CdSe/ZnS are confirmed by X-ray photon spectroscopy. The sensors are studied for sensing of hydrogen ions concentration in different buffer solutions at broad pH range of 2 to 12. The QD sensors show improved sensitivity (38 to 55 mV/pH) as compared to bare SiO₂ sensor (36 to 23 mV/pH) with time period of 0 to 24 months, owing to the reduction of defects in the QDs. Therefore, the differential sensitivity of the QD sensors with respect to the bare SiO₂ sensors is improved from 2 to 32 mV/pH for the time period of 0 to 24 months. After 24 months, the sensitivity of the QD sensors is close to ideal Nernstian response with good linearity of 99.96%. Stability and repeatability of the QD sensors show low drift (10 mV for 10 cycles) as well as small hysteresis characteristics (<10 mV). This QD sensor is very useful for future human disease diagnostics.     

混合溶剂中十八胺含量对CdSe量子点发光性能的影响

利用高温溶剂法,在十八胺(ODA)和十八醇(OD)混合溶剂中合成了CdSe量子点(QDs),表征了在不同反应时间和不同ODA与OD质量比条件下制备的QDs粒径和光学性质。结果表明,在混合溶剂中不仅可以制备出分散性良好、粒径均匀的QDs,而且还能获得高量子效率的产物;ODA含量变化基本不影响QDs的初始成核粒径,但对量子效率有很明显的影响,ODA含量的增加对获得高量子效率的产物有利。     

A sensitive electrochemical aptasensor based on water soluble CdSe quantum dots (QDs) for thrombin determination

A novel aptamer biosensor with easy operation and good sensitivity, specificity, stability and reproducibility was developed by immobilizing the aptamer on water soluble CdSe quantum dots (QDs) modified on the top of the glassy carbon electrode (GCE). Methylene blue (MB) was intercalated into the aptamer sequence and used as an electrochemical marker. CdSe QDs improved the electrochemical signal because of their larger surface area and ion centers of CdSe QDs may also had a major role on amplifying the signal. The higher ion concentration caused more combination of aptamer which caused larger signal. The thrombin was detected by differential pulse voltammetry (DPV) quantitatively. Under optimal conditions, the two linear ranges were obtained from 3 to 13 μg mL⁻¹ and from 14 to 31 μg mL⁻¹, respectively. The detection limit was 0.08 μg mL⁻¹ at 3σ. The constructed biosensor had better responses compared with that in the absence of the CdSe QDs immobilizing. The control experiment was also carried out by using BSA, casein and IgG in the absence of thrombin. The results showed that the aptasensor had good specificity, stability and reproducibility to the thrombin. Moreover, the aptasensor could be used for detection of real sample with consistent results in comparison with those obtained by fluorescence method which could provide a promising platform for fabrication of aptamer based biosensors.     

硒化镉量子点的合成及表征

在氩气条件下和非配位溶剂十八烯（ODE）中,利用单质Se和CdO在油酸（OA）配体中,高温成核,低温增长合成量子点CdSe。利用紫外吸收光谱和荧光对量子点进行表征和分析,初步产物的荧光谱图呈现两个荧光发射峰,分别为短波处较窄的带边发射和长波处较宽的缺陷发射。利用一种修饰剂对量子点表面进行修饰,有效的消除缺陷发射,修饰后的量子点在荧光谱图中表现为仅有一个发射峰位,峰位处于410nm左右。在紫外灯照射下显示紫色。     

Fabrication of surface‐modified CdSe quantum dots by self‐assembly of a functionalizable comb polymer

A facile approach is proposed for the fabrication of surface‐modified CdSe quantum dots (QDs) with compatibility with various media and better dispersibility by self‐assembly of a functionalizable comb polymer. The comb polymer was prepared from the reaction between the acyl chloride groups in poly(acryloyl chloride) and the hydroxyl groups in 1‐octadecanol. With the combination of the compatibility and entanglement of the aliphatic chain in 1‐octadecanol and similar aliphatic chain in oleic acid ligand of QDs, the comb polymer could cap on the QDs and thus endow them with functional groups. The structure of such a polymer was investigated using Fourier transform infrared spectroscopy. According to the reactivity of remaining acyl chloride groups in the comb polymer, the polymer ligands could be tailored to be various structures, and then lipophilic, hydrophilic and functional QDs were obtained. The fluorescence properties of the surface‐modified QDs were investigated, and the morphologies and dispersions of different kinds of surface‐modified QDs were characterized using transmission electron microscopy. Finally, homogeneous and stable dispersions of QDs in various media could be realized by adjusting the structure of the comb polymer. Copyright © 2010 Society of Chemical Industry     

Effect of CdSe quantum dots on the performance of hybrid solar cells based on ZnO nanorod arrays

This paper reports the fabrication and interface modification of hybrid inverted solar cells based on ZnO nanorod arrays and poly (3-hexylthiophene). CdSe quantum dots (QDs) are grafted to the ZnO nanorod array successfully by bifunctional molecule mercaptopropionic acid to enhance the device performance. The power conversion efficiency of the device is increased by 109% from 0.11% to 0.23% under simulated 1 sun AM 1.5 solar illumination at 100 mW/cm² after the modification. The grafting of CdSe QDs effectively enhanced the excition generation and dissociation on the organic/inorganic interface. This work may provide a general method for increasing the efficiency of organic–inorganic hybrid solar cells by interface modification.