InP胶体量子点的合成及光谱性质

以三辛基氧化膦(TOPO)作为溶剂,利用无水InCl3和P(Si(CH3)3)3之间的脱卤硅烷基反应合成了InP胶体量子点.其中,TOPO既作为反应溶剂又作为量子点的包覆剂和稳定剂,在反应后期加入十二胺作为表面活性剂.利用粉末X射线衍射仪及透射电子显微镜测量了量子点的结晶性、晶格结构、晶粒尺寸、表面形貌以及晶粒尺寸分布,利用光致发光(PL)光谱仪和紫外可见分光光度计分析了其光学性质.测试结果显示,量子点具有较好的结晶性及一定的尺寸分布,平均直径为2.5nm,标准偏差为7.4%,表现出明显的量子限制效应.     

InP胶体量子点的合成及光谱性质

以三辛基氧化膦(TOPO)作为溶剂,利用无水InCl3和P(Si(CH3)3)3之间的脱卤硅烷基反应合成了InP胶体量子点.其中,TOPO既作为反应溶剂又作为量子点的包覆剂和稳定剂,在反应后期加入十二胺作为表面活性剂.利用粉末X射线衍射仪及透射电子显微镜测量了量子点的结晶性、晶格结构、晶粒尺寸、表面形貌以及晶粒尺寸分布,利用光致发光(PL)光谱仪和紫外可见分光光度计分析了其光学性质.测试结果显示,量子点具有较好的结晶性及一定的尺寸分布,平均直径为2.5nm,标准偏差为7.4%,表现出明显的量子限制效应.     

Integrative Self‐Assembly of Graphene Quantum Dots and Biopolymers into a Versatile Biosensing Toolkit

Hybrid self‐assembly has become a reliable approach to synthesize soft materials with multiple levels of structural complexity and synergistic functionality. In this work, photoluminescent graphene quantum dots (GQDs, 2–5 nm) are used for the first time as molecule‐like building blocks to construct self‐assembled hybrid materials for label‐free biosensors. Ionic self‐assembly of disc‐shaped GQDs and charged biopolymers is found to generate a series of hierarchical structures that exhibit aggregation‐induced fluorescence quenching of the GQDs and change the protein/polypeptide secondary structure. The integration of GQDs and biopolymers via self‐assembly offers a flexible toolkit for the design of label‐free biosensors in which the GQDs serve as a fluorescent probe and the biopolymers provide biological function. The versatility of this approach is demonstrated in the detection of glycosaminoglycans (GAGs), pH, and proteases using three strategies: 1) competitive binding of GAGs to biopolymers, 2) pH‐responsive structural changes of polypeptides, and 3) enzymatic hydrolysis of the protein backbone, respectively. It is anticipated that the integrative self‐assembly of biomolecules and GQDs will open up new avenues for the design of multifunctional biomaterials with combined optoelectronic properties and biological applications.     

Passivating {100} Facets of PbS Colloidal Quantum Dots via Perovskite Bridges for Sensitive and Stable Infrared Photodiodes

Solution-processed PbS colloidal quantum dots (CQDs) are promising optoelectronic materials for next-generation infrared imagers due to their monolithic integratability with silicon readout circuit and tunable bandgap controlled by CQDs size. However, large-size PbS CQDs (diameter >4 nm) for longer shortwave-infrared photodetection consist mainly of {100} facets with incomplete surface passivation and unsatisfied stability. Here, it is reported that perovskite-bridged PbS CQDs, in which the {100} facets of the CQDs are epitaxially bridged with CsPbI_3–xBr_x perovskite, can achieve improved passivation and enhanced stability in comparison with the traditional strategies. The resultant infrared CQDs photodiodes exhibit significantly reduced dark current, nearly 50% enhanced photoresponse, and improved work stability. These superior properties synergistically produce the most balanced performance (with a high −3 dB bandwidth of 42 kHz and an impressive specific detectivity of 6.2 × 10¹² Jones) among the reported CQDs photodetectors.     

Highly Stable Colloidal “Giant” Quantum Dots Sensitized Solar Cells

Colloidal quantum dots (QDs) are widely studied due to their promising optoelectronic properties. This study explores the application of specially designed and synthesized “giant” core/shell CdSe/(CdS)_x QDs with variable CdS shell thickness, while keeping the core size at 1.65 nm, as a highly efficient and stable light harvester for QD sensitized solar cells (QDSCs). The comparative study demonstrates that the photovoltaic performance of QDSCs can be significantly enhanced by optimizing the CdS shell thickness. The highest photoconversion efficiency (PCE) of 3.01% is obtained at optimum CdS shell thickness ≈1.96 nm. To further improve the PCE and fully highlight the effect of core/shell QDs interface engineering, a CdSe_x S_1?x interfacial alloyed layer is introduced between CdSe core and CdS shell. The resulting alloyed CdSe/(CdSe_x S_1?x )₅/(CdS)₁ core/shell QD‐based QDSCs yield a maximum PCE of 6.86%, thanks to favorable stepwise electronic band alignment and improved electron transfer rate with the incorporation of CdSe_x S_1?x interfacial layer with respect to CdSe/(CdS)₆ core/shell. In addition, QDSCs based on “giant” core/CdS‐shell or alloyed core/shell QDs exhibit excellent long‐term stability with respect to bare CdSe‐based QDSCs. The giant core/shell QDs interface engineering methodology offers a new path to improve PCE and the long‐term stability of liquid junction QDSCs.     

GaAs图形衬底上InAs量子点生长停顿的动力学蒙特卡罗模拟

采用动力学蒙特卡罗模拟方法对GaAs图形衬底上自组织生长InAs量子点的停顿过程进行了研究．用衬底束缚能的表面分布模拟衬底图形，考察生长之后的停顿时间对量子点形成的影响．结果表明，合适的停顿时间使图形衬底上的量子点分布更趋规则化，对量子点的定位生长有积极的影响．     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.     

Controllable Patterning of Different Cells Via Optical Assembly of 1D Periodic Cell Structures

Flexible patterning of different cells into designated locations with direct cell–cell contact at single‐cell patterning precision and control is of great importance, however challenging, for cell patterning. Here, an optical assembly method for patterning of different types of cells via direct cell–cell contact at single‐cell patterning precision and control is demonstrated. Using Escherichia coli and Chlorella cells as examples, different cells are flexibly patterned into 1D periodic cell structures (PCSs) with controllable configurations and lengths, by periodically connecting one type of cells with another by optical force. The patterned PCSs can be flexibly moved and show good light propagation ability. The propagating light signals can be detected in real‐time, providing new opportunities for the detection of transduction signals among patterned cells. This patterning method is also applicable for cells of other kinds, including mammalian/human cells.     

Cocatalyst‐Free Photocatalysts for Efficient Visible‐Light‐Induced H2 Production: Porous Assemblies of CdS Quantum Dots and Layered Titanate Nanosheets

Highly efficient, visible‐light‐induced H₂ generation can be achieved without the help of a Pt cocatalyst by new hybrid photocatalysts, in which CdS quantum dots (QDs) (particle size ≈2.5 nm) are incorporated in the porous assembly of sub‐nanometer‐thick layered titanate nanosheets. Due to the very‐limited crystal dimension of component semiconductors, the electronic structure of CdS QDs is strongly coupled with that of the layered titanate nanosheets, leading to an efficient electron transfer between them and the enhancement of the CdS photostability. As a consequence of the promoted electron transfer, the photoluminescence of CdS QDs is nearly quenched after hybridization, indicating the almost‐suppression of electron‐hole recombination. These Pt‐cocatalyst‐free, CdS‐layered titanate nanohybrids show much‐higher photocatalytic activity for H₂ production than the precursor CdS QDs and layered titanate, which is due to the increased lifetime of the electrons and holes, the decrease of the bandgap energy, and the expansion of the surface area upon hybridization. The observed photocatalytic efficiency of these Pt‐free hybrids (≈1.0 mmol g^?1 h^?1) is much greater than reported values of other Pt‐free CdS‐TiO₂ systems. This finding highlights the validity of 2D semiconductor nanosheets as effective building blocks for exploring efficient visible‐light‐active photocatalysts for H₂ production.     

Facile Synthesis of Graphene Quantum Dots from 3D Graphene and their Application for Fe3+ Sensing

Owing to their small size, biocompatibility, unique and tunable photoluminescence, and physicochemical properties, graphene quantum dots (GQDs) are an emerging class of zero‐dimensional materials promising a wide spectrum of novel applications in bio‐imaging, optical, and electrochemical sensors, energy devices, and so forth. Their widespread use, however, is largely limited by the current lack of high yield synthesis methods of high‐quality GQDs. In this contribution, a facile method to electrochemically exfoliate GQDs from three‐dimensional graphene grown by chemical vapor deposition (CVD) is reported. Furthermore, the use of such GQDs for sensitive and specific detection of ferric ions is demonstrated.     

Assembly and Characterizations of Bifunctional Fluorescent and Magnetic Microneedles With One Decade Length Tunability

This report presents the fabrication of bifunctional magnetic and fluorescent microneedles (µNDs) made of a ternary mixture of magnetic nanoparticles (NPs), quantum dots (QDs), and polyelectrolyte. The assembly relies on the electrostatic complexation of negatively charged NPs with positively charged polymer strands and is controlled by the charge ratio between the nanoparticle building blocks and the polymer mortar. The resulting 1D objects can be actuated using an external magnetic field and can be imaged using fluorescence microscopy, thanks to the fluorescent and superparamagnetic properties inherited from their NP constituents. Using a combination of core and surface characterizations and a state‐of‐the‐art image analysis algorithm, the dependence of the brightness and length on the ternary composition is thoroughly investigated. In particular, statistics on hundreds of µNDs with a range of compositions show that the µNDs have a log‐lormal length distribution and that their mean length can be robustly tuned in the 5–50 µm range to match the relevant length scales of various applications in micromixing, bioassays or biomechanics.     

Solvent‐Polarity‐Engineered Controllable Synthesis of Highly Fluorescent Cesium Lead Halide Perovskite Quantum Dots and Their Use in White Light‐Emitting Diodes

Cesium lead halide quantum dots (QDs) have tunable photoluminescence that is capable of covering the entire visible spectrum and have high quantum yields, which make them a new fluorescent materials for various applications. Here, the synthesis of CsPbX₃ (X = Cl, Br, I, or mixed Cl/Br and Br/I) QDs by direct ion reactions in ether solvents is reported, and for the first time the synergetic effects of solvent polarity and reaction temperature on the nucleation and growth of QDs are demonstrated. The use of solvent with a low polarity enables controlled growth of QDs, which facilitates the synthesis of high‐quality CsPbX₃ QDs with broadly tunable luminescence, narrow emission width, and high quantum yield. A QD white LED (WLED) is demonstrated by coating the highly fluorescent green‐emissive CsPbBr₃ QDs together with red phosphors on a blue InGaN chip, which presents excellent warm white light emission with a high rendering index of 93.2 and color temperature of 5447 K, suggesting the potential applications of highly fluorescent cesium lead halide perovskite QDs as an alternative color converter in the fabrication of WLEDs.     

CdTe Quantum Dots/Layered Double Hydroxide Ultrathin Films with Multicolor Light Emission via Layer‐by‐Layer Assembly

Quantum dots (QDs) luminescent films have broad applications in optoelectronics, solid‐state light‐emitting diodes (LEDs), and optical devices. This work reports the fabrication of multicolor‐light‐emitting ultrathin films (UTFs) with 2D architecture based on CdTe QDs and MgAl layered double hydroxide (LDH) nanosheets via the layer‐by‐layer deposition technique. The hybrid UTFs possess periodic layered structure, which is verified by X‐ray diffraction. Tunable light emission in the red‐green region is obtained by changing the particle size of QDs (CdTe‐535 QDs and CdTe‐635 QDs with green and red emision respectively), assembly cycle number, and sequence. Moreover, energy transfer between CdTe‐535 QDs and CdTe‐635 QDs occurs based on the fluorescence resonance energy transfer (FRET), which greatly enhances the fluorescence efficiency of CdTe‐635 QDs. In addition, a theoretical study based on the Förster theory and molecular dynamics (MD) simulations demonstrates that CdTe QDs/LDH UTFs exhibit superior capability of energy transfer owing to the ordered dispersion of QDs in the 2D LDH matrix, which agrees well with the experimental results. Therefore, this provides a facile approach for the design and fabrication of inorganic‐inorganic luminescent UTFs with largely enhanced luminescence efficiency as well as stability, which can be potentially applied in multicolor optical and optoelectronic devices.     

Nanomanufacturing with DNA Origami: Factors Affecting the Kinetics and Yield of Quantum Dot Binding

Molecularly directed self‐assembly has the potential to become a nanomanufacturing technology if the critical factors governing the kinetics and yield of defect‐free self‐assembled structures can be understood and controlled. The kinetics of streptavidin‐functionalized quantum dots binding to biontinylated DNA origami are quantitatively evaluated and to what extent the reaction rate and binding efficiency are controlled by the valency of the binding location, the biotin linker length, and the organization, and spacing of the binding locations on the DNA is shown. Yield improvement is systematically determined as a function of the valency of the binding locations and as a function of the quantum dot spacing. In addition, the kinetic studies show that the binding rate increases with increasing linker length, but that the yield saturates at the same level for long incubation times. The forward and backward reaction rate coefficients are determined using a nonlinear least squares fit to the measured binding kinetics, providing considerable physical insight into the factors governing this type of self‐assembly process. It is found that the value of the dissociation constant, K_d, for the DNA–nanoparticle complex considered here is up to seven orders of magnitude larger than that of the native biotin–streptavidin complex. This difference is attributed to the combined effect that the much larger size of the DNA origami and the quantum dot have on the translational and rotational diffusion constants.     

Targeting of Cancer Cells Using Quantum Dot–Polypeptide Hybrid Assemblies That Function as Molecular Imaging Agents and Carrier Systems

A highly tunable quantum dot (QD)–polypeptide hybrid assembly system with potential uses for both molecular imaging and delivery of biomolecular cargo to cancer cells is reported. The tunability of the assembly system, its application for imaging cancer cells, and its ability to carry a biomolecule are demonstrated. The assemblies are formed through the self‐assembly of carboxyl‐functionalized QDs and poly(diethylene glycol‐L ‐lysine)‐poly(L ‐lysine) (PEGLL‐PLL) diblock copolypeptide molecules, and they are modified with peptide ligands containing a cyclic arginine‐glycine‐aspartate [c(RGD)] motif that has affinity for αvβ3 and αvβ5 integrins overexpressed on the tumor vasculature. To illustrate the tunability of the QD‐polypeptide assembly system, it is shown that binding to U87MG glioblastoma cells can be modulated and optimized by changing either the conditions under which the assemblies are formed or the relative lengths of the PEGLL and PLL blocks in the PEGLL‐PLL molecules. The optimized c(RGD)‐modified assemblies bind integrin receptors on U87MG cells and are endocytosed, as demonstrated by flow cytometry and live‐cell imaging. Binding specificity is confirmed by competition with an excess of free c(RGD) peptide. Finally, it is shown that the QD–polypeptide assemblies can be loaded with fluorescently labeled ovalbumin, as a proof‐of‐concept for their potential use in biomolecule delivery.     

On‐the‐Spot Immobilization of Quantum Dots,Graphene Oxide,and Proteins via Hydrophobins

Class I hydrophobin Vmh2, a peculiar surface active and versatile fungal protein, is known to self‐assemble into chemically stable amphiphilic films, to be able to change wettability of surfaces, and to strongly adsorb other proteins. Herein, a fast, highly homogeneous and efficient glass functionalization by spontaneous self‐assembling of Vmh2 at liquid–solid interfaces is achieved (in 2 min). The Vmh2‐coated glass slides are proven to immobilize not only proteins but also nanomaterials such as graphene oxide (GO) and quantum dots (QDs). As models, bovine serum albumin labeled with Alexa 555 fluorophore, anti‐immunoglobulin G antibodies, and cadmium telluride QDs are patterned in a microarray fashion in order to demonstrate functionality, reproducibility, and versatility of the proposed substrate. Additionally, a GO layer is effectively and homogeneously self‐assembled onto the studied functionalized surface. This approach offers a quick and simple alternative to immobilize nanomaterials and proteins, which is appealing for new bioanalytical and nanobioenabled applications.     

Uniformly Confined Germanium Quantum Dots in 3D Ordered Porous Carbon Framework for High‐Performance Li‐ion Battery

Although abundant germanium (Ge)‐based anode materials have been explored to obtain high specific capacity, high rate performance, and long charge/discharge lifespans for lithium‐ion batteries (LIBs), their performances are still far from satisfactory due to the intrinsic defects of Ge and the relatively intricate anode structure. To work out these issues, a 3D ordered porous N‐doped carbon framework with Ge quantum dots uniformly embedded (3DOP Ge@N? C) as a binder‐free anode for LIBs via a facile polystyrene colloidal nanospheres template‐confined strategy is proposed. This unique structure not only facilitates Li‐ion diffusion and electron transport that can guarantee rapid de/alloying reaction, but also alleviates the huge volume changes during reactions and improves cycling stability. Notably, the resulting anode delivers a high specific reversible capacity (≈1160 mA h g^?1 at 1 A g^?1), superior rate properties (exceeding 500 mA h g^?1 at 40 A g^?1), and excellent cycling stability (over 90% capacity retention after 1200 cycles even at 5 A g^?1). Furthermore, both the 3DOP Ge@N? C anode with high areal mass loading (up to 8 mg cm^?2) and the full cell coupled with LiFePO₄ cathode display high capacity and cycling stability, further indicative of the favorable real‐life application prospects for high‐energy LIBs.