Synthesis and photoluminescent properties of ZnO:Cu/ZnO core/shell nanocrystals

ZnO:Cu/ZnO core/shell nanocrystals are synthesized by a two-step solution-phase process. The morphology, structure and optical properties of the samples are detected by scanning electron microscopy, Raman, absorption and luminescence spectroscopy. The increase of particle size confirms the growth of ZnO shell. The segregation of CuO phase observed in ZnO: Cu core is not detected in ZnO:Cu/ZnO core/shell nanocrystals from Raman spectra. It is suggested that some Cu ions can be segregated from ZnO nanocrystals, and the separated Cu ions can be incorporated inside ZnO shell after the growth of ZnO shell. The visible emission mechanism is discussed in detail, and the photoluminescence analysis indicates that the core/shell structure helps to eliminate the surface-related emission.     

Reconfigurable Anisotropic Coatings via Magnetic Field‐Directed Assembly and Translocation of Locking Magnetic Chains

A method for the generation of remotely reconfigurable anisotropic coatings is developed. To form these coatings, locking magnetic nanoparticles (LMNPs) made of a superparamagnetic core and a two‐component polymer shell are employed. Two different polymers form phase‐separated coaxial shells. The outer shell provides repulsive interactions between the LMNPs while the inner shell exerts attractive forces between the particles. Applying a non‐uniform magnetic field, one gathers the particles together, pushing them to come in contact when the internal shells could effectively hold the particles together. When the magnetic field is turned off, the particles remain locked due to these strong interactions between internal shells. The shells are thus made stimuli‐responsive, so this locking can be made reversible and the chains can be disintegrated on demand. In a non‐uniform magnetic field, the assembled chains translocate, bind to the solid substrate and form anisotropic coatings with a “locked” anisotropic structure. The coatings can be constructed, aligned, realigned, degraded, and generated again on demand by changing the magnetic field and particle environment. The mechanism of the coating formation is explained using experimental observations and a theoretical model.     

Synthesis of Au–CdS Core–Shell Hetero‐Nanorods with Efficient Exciton–Plasmon Interactions

The synthesis of large lattice mismatch metal‐semiconductor core–shell hetero‐nanostructures remains challenging, and thus the corresponding optical properties are seldom discussed. Here, we report the gold‐nanorod‐seeded growth of Au–CdS core–shell hetero‐nanorods by employing Ag₂S as an interim layer that favors CdS shell formation through a cation‐exchange process, and the subsequent CdS growth, which can form complete core–shell structures with controllable shell thickness. Exciton–plasmon interactions observed in the Au–CdS nanorods induce shell thickness‐tailored and red‐shifted longitudinal surface plasmon resonance and quenched CdS luminescence under ultraviolet light excitation. Furthermore, the Au–CdS nanorods demonstrate an enhanced and plasmon‐governed two‐photon luminescence under near‐infrared pulsed laser excitation. The approach has potential for the preparation of other metal‐semiconductor hetero‐nanomaterials with complete core–shell structures, and these Au–CdS nanorods may open up intriguing new possibilities at the interface of optics and electronics.     

Self‐Assembly of Tunable Nanocrystal Superlattices Using Poly‐(NIPAM) Spacers

Understanding and controlling 3D nanocrystal self‐assembly is a fundamental challenge in materials science. Assembly enables the unique optical and electronic properties of nanocrystals to be exploited in macroscopic materials, and also opens up the possibility to couple the optical response of nanocrystals to the optical modes of the superlattice. To date, assembly of such nanocrystal superlattices (NCSL) has focussed on fixed, close packed structures with particle separations of just 1–3 nm. To achieve highly crystalline structures with tunable optical response, the nanocrystal interparticle separation needs to be precise and easily variable but >50 nm. Here, we show the preparation of nanocrystal superlattices with spacings of 50–500 nm assembled from gold‐poly‐N‐isopropylacrylamide core‐shell particles and the characterization of their fascinating diffraction behavior by means of UV‐vis spectroscopy. These nanocrystal superlattices exhibit pronounced diffraction in the visible (440‐560 nm) with peak half‐widths of the order of 10 nm. The position of the Bragg peak is simply tuned by adjusting the particle volume fraction. Due to the thermoresponsive nature of the polymer shell, temperature is used to initiate crystallization or melting of the superlattice. Heating and cooling cycles cause highly reversible melting/recrystallization in less than a minute.     

Core/Shell Metal Halide Perovskite Nanocrystals for Optoelectronic Applications

Core/shell structured metal halide perovskite nanocrystals (NCs) are emerging as a type of material with remarkable optical and electronic properties. Research into this field has been developing and expanding rapidly in recent years, with significant advances in the studies of the shell growth mechanism and in understanding of properties of these materials. Significant enhancement of both the stability and the optical performance of core/shell perovskite NCs are of particular importance for their applications in optoelectronic technologies. In this review, the recent advances in core/shell structured perovskite NCs are summarized. The band structures and configurations of core/shell perovskite NCs are elaborated, the shell classification and shell engineering approaches, such as perovskites and their derivative shells, semiconductor shell, oxide shell, polymer shell, etc. are reviewed, and the shell growth mechanisms are discussed. The prospective of these NCs in lighting and displays, solar cells, photodetectors, and other devices is discussed in the light of current knowledge, remaining challenges, and future opportunities.     

包覆较厚介质层的金属铜球在聚焦光场中的捕获特性研究

基于核(金属)/壳(介质)微球的单光束梯度阱模型,计算了外面包覆较厚聚苯乙烯的铜微球在聚焦光场中的轴向散射力、梯度力以及合力,分析了表面被高度氧化的铜微球的轴向捕获力。不同于纯金属米氏粒子,外层包覆较厚介质材料的金属粒子在聚焦光场中容易被捕获但不能被捕获在聚焦光束的高强度区域。光学微操作实验显示:高度氧化的铜微球能被聚焦的高斯光束捕获并可以在平面内移动。理论和实验结果便于研究核壳结构金属微粒的光学特性,进一步拓展了光镊技术的应用范围。     

Ordered 3D Thin‐Shell Nanolattice Materials with Near‐Unity Refractive Indices

The refractive indices of naturally occurring materials are limited, and there exists an index gap between indices of air and available solid materials. With many photonics and electronics applications, there has been considerable effort in creating artificial materials with optical and dielectric properties similar to air while simultaneously being mechanically stable to bear load. Here, a class of ordered nanolattice materials consisting of periodic thin‐shell structures with near‐unity refractive index and high stiffness is demonstrated. Using a combination of 3D nanolithography and atomic layer deposition, these ordered nanostructured materials have reduced optical scattering and improved mechanical stability compared to existing randomly porous materials. Using ZnO and Al₂O₃ as the building materials, refractive indices from 1.3 down to 1.025 are achieved. The experimental data can be accurately described by Maxwell Garnett effective media theory, which can provide a guide for index design. The demonstrated low‐index, low‐scattering, and high‐stiffness materials can serve as high‐quality optical films in multilayer photonic structures, waveguides, resonators, and ultra‐low‐k dielectrics.     

Core–Shell Zeolite Microcomposites

Core–shell zeolite composites possessing a core and a shell of different zeolite structure types have been synthesized. A characteristic feature of the obtained composites is the relatively large single‐crystal core and the very thin polycrystalline shell. The incompatibility between the core crystals and the zeolite precursor mixture yielding the shell layer has been circumvented by the adsorption of nanoseeds on the core surface, which induced the crystallization of the shell. The pretreated core crystals are subsequently subjected to a continuous growth in a zeolite precursor mixture. The feasibility of this synthetic approach has been exemplified by the preparation of core–shell β‐zeolite–silicalite‐1 composites. The synthesized composites have been characterized using X‐ray diffraction, high‐resolution transmission electron microscopy, and scanning electron microscopy. The integrity of the shell layer has been tested via N₂‐adsorption measurements on materials comprising a calcined core (β‐zeolite) and a non‐calcined tetrapropylammonium (TPA)‐containing shell, the latter being non‐permeable for the N₂ molecules. These measurements have shown that 86 % of the β‐zeolite crystals are covered with a defect‐free TPA–silicalite‐1 shell after a single hydrothermal treatment, while after three consecutive crystallization steps this value reaches 99 %. The shell integrity of the calcined composite has been studied by the adsorption of butane, toluene, and 1,3,5‐trimethylbenzene, which confirmed the superior performance of the triple‐shell composites.     

Facile Methods to Coat Polystyrene and Silica Colloids with Metal

To avoid the complex core surface functionalization or pretreatment that is necessary in order to coat latex and silica colloids with a uniform, complete metal shell, the solvent‐assisted route has been explored to prepare a complete metal (Ag or Au) shell with controlled thickness on polystyrene (PS) colloids and the electroless plating approach, based on electrostatic attraction, has been explored to prepare a complete silver shell with controlled thickness on silica colloids. Without any additional surface treatment, the as‐prepared complex core–shell colloids can be crystallized directly into long‐range‐ordered structures with photonic bandgaps, as reported here for the first time. These ordered structures may find potential applications as substrates or physical systems for the enhancement of Raman scattering studies, besides applications as photonic crystals. The optical plasmon resonance of the composite core–shell colloids changes with metal shell thickness, the wavelength varying over hundreds of nanometers. Our coating routes are facile and versatile, and can be extended to coat PS and silica colloids with any other metal whose ion or complex can be reduced in solution.     

Thermally induced whispering gallery mode laser in MEH-PPV solutions

We report on thermally activated whispering gallery laser modes of a solution of MEH-PPV conjugated polymer supported by a silica optical fiber. The viscosity of the polymer solution gives place to a thin shell of the gain solution around the fiber driven by capillary action. Whispering gallery modes (WGMs) are thermally induced by a decrease in the refractive index of the polymer solution under intense optical pumping. The laser emission is produced because the evanescent waves of the WGMs couple the surrounding gain medium. These results support the use of conjugated polymers in optofluidic laser systems and highlight the importance of physicochemical properties, such as viscosity and optically induced heating, on the performance of the devices.     

Addressing Particle Compositional Heterogeneities in Super-Resolution-Enhanced Live-Cell Ratiometric pH Sensing with Ultrasmall Fluorescent Core–Shell Aluminosilicate Nanoparticles

The interrogation of metabolic parameters like pH in live-cell experiments using optical super-resolution microscopy (SRM) remains challenging. This is due to a paucity of appropriate metabolic probes enabling live-cell SRM-based sensing. Here, ultrasmall fluorescent core–shell aluminosilicate nanoparticle sensors (FAM–ATTO647N aC′ dots) that covalently encapsulate a reference dye (ATTO647N) in the core and a pH-sensing moiety (FAM) in the shell are introduced. Only the reference dye exhibits optical blinking enabling live-cell stochastic optical reconstruction microscopy (STORM). Using data from cells incubated for 60 min with FAM–ATTO647N aC′ dots, pixelated information from total internal reflection fluorescence (TIRF) microscopy-based ratiometric sensing can be combined with that from STORM-based localizations via the blinking reference dye in order to enhance the resolution of ratiometric pH sensor maps beyond the optical diffraction limit. A nearest-neighbor interpolation methodology is developed to quantitatively address particle compositional heterogeneity as determined by separate single-particle fluorescence imaging methods. When combined with STORM-based estimates of the number of particles per vesicle, vesicle size, and vesicular motion as a whole, this analysis provides detailed live-cell spatial and functional information, paving the way to a comprehensive mapping and understanding of the spatiotemporal evolution of nanoparticle processing by cells important, e.g., for applications in nanomedicine.     

Responsive Macroscopic Materials From Self‐Assembled Cross‐Linked SiO2‐PNIPAAm Core/Shell Structures

A way to obtain macroscopic responsive materials from silicon‐oxide polymer core/shell microstructures is presented. The microparticles are composed of a 60 nm SiO₂‐core with a random copolymer corona of the temperature responsive poly‐N‐isopropylacrylamide (PNIPAAm) and the UV‐cross‐linkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide. The particles shrink upon heating and form a stable gel in both water and tetrahydrofuran (THF) at 3–5 wt% particle content. Cross‐linking the aqueous gel results in shrinkage when the temperature is increased above the lower critical solution temperature and it regains its original size upon cooling. By freeze drying with subsequent UV irradiation, thin stable layers are prepared. Stable fibers are produced by extruding a THF gel into water and subsequent UV irradiation, harnessing the cononsolvency effect of PNIPAAm in water/THF mixtures. The temperature responsiveness translates to the macroscopic materials as both films and fibers show the same collapsing behavior as the microcore/shell particle. The collapse and re‐swelling of the materials is related to the expelling and re‐uptake of water, which is used to incorporate gold nanoparticles into the materials by a simple heating/cooling cycle. This allows for future applications, as various functional particles (antibacterial, fluorescence, catalysis, etc.) can easily be incorporated in these systems.     

The Analysis of Impedance Spectra for Core–Shell Microstructures: Why a Multiformalism Approach is Essential

The impedance response of a core–shell microstructure with 80% core volume fraction has been simulated using finite‐element modeling and compared to two equivalent circuits for a wide range of shell permittivity and conductivity values. Different equivalent circuits, corresponding to different variants of the well‐known brick layer model, are applicable for different combinations of material properties in the microstructure. When the shell has a similar conductivity or permittivity to the core, adding a parallel pathway increases the accuracy of the fit by ≈±10%. When both the conductivity and permittivity values of the core and shell regions are different the series circuit is a better fit. This is confirmed by multiformalism impedance analysis, which reveals features in the data that are not apparent using a single formalism. Finally, the conductivity and permittivity values for both the shell and core are extracted from the simulated spectra using all formalisms and compared to the original input values. The accuracy of the extracted values often depends on the impedance formalism used. It is concluded that impedance spectroscopy data must be analyzed using multiple formalisms when considering core–shell microstructures.     

Cover Picture: A Hierarchically Structured Ni(OH)2 Monolayer Hollow‐Sphere Array and Its Tunable Optical Properties over a Large Region (Adv. Funct. Mater. 4/2007)

The fabrication of hierarchically structured Ni(OH)₂ monolayer hollow‐sphere arrays with the shell composed of building blocks of nanoflakelets is reported on p. 644 by Weiping Cai and co‐workers. The morphology can be easily controlled by the synthesis parameters, and the arrays show a tunable optical transmission stop band. Tuning can be achieved by changing the size or morphology of the hollow spheres. Such arrays may have potential applications in optical devices, photonic crystals, and as sensors for gas detection. The fabrication of a hierarchically structured Ni(OH)₂ monolayer hollow‐sphere array with the shell composed of building blocks of nanoflakelets is demonstrated based on a colloidal monolayer and electrochemical deposition. The morphology can be easily controlled by the colloidal monolayer and deposition parameters. Importantly, such monolayer hollow‐sphere array shows a morphology‐ and size‐dependent tunable optical transmission stop band. This stop band can be easily tuned from 455–1855 nm by changing the size of the hollow spheres between 1000 and 4500 nm, and also fine‐adjusted by changing the deposition time. The array exhibits a nearly incident‐angle‐independent position of the stop band that 3D photonic crystals do not possess. This structure may have potential applications in optical devices, photonic crystals, and sensors for gas detection.     

灰霾期间硫酸盐包裹沙尘气溶胶粒子的光学特性研究

灰霾期间硫酸盐与沙尘矿物颗粒表面经过系列化学反应形成复杂的混合状态,为气溶胶光学性质模拟带来很大困难。因此,厘清硫酸盐壳对沙尘矿物颗粒光学特性的影响机制具有重要意义。文中根据灰霾期间硫酸盐与沙尘矿物颗粒反应过程中的混合结构变化,建立了沙尘-硫酸盐颗粒的核壳椭球结构模型。采用T矩阵方法,研究了四波段条件（0.44、0.675、0.87、1.02 μm）下,混合比对单分散系沙尘-硫酸盐粒子光学特性的影响。结果表明:混合比对沙尘-硫酸盐粒子光学特性的影响主要在Mie散射区,在瑞利散射区,混合比对粒子光学特性影响不大。同时研究结果还表明,当混合比小于0.3时,硫酸盐壳在粒子散射特性中占主导地位;当混合比大于0.7时,粒子散射特性主要受沙尘核的影响;在此区间内,粒子散射特性由硫酸盐与沙尘共同影响,并会出现强于（或弱于）任何一种纯颗粒物的现象。该研究对理解灰霾老化期间单颗粒气溶胶混合结构及其光学特性具有重要意义。     

Laser‐Activatible PLGA Microparticles for Image‐Guided Cancer Therapy In Vivo

Poly(lactide‐co‐glycolic acid) (PLGA) particles are biocompatible and bio­degradable, and can be used as a carrier for various chemotherapeutic drugs, imaging agents and targeting moieties. Micrometer‐sized PLGA particles were synthesized with gold nanoparticles and DiI dye within the PLGA shell, and perfluorohexane liquid (PFH) in the core. Upon laser irradiation, the PLGA shell absorbs the laser energy, activating the liquid core (liquid conversion to gas). The rapidly expanding gas is expelled from the particle, resulting in a microbubble; this violent process can cause damage to cells and tissue. Studies using cell cultures show that PLGA particles phagocytosed by single cells are consistently vaporized by laser energies of 90 mJ cm^?2, resulting in cell destruction. Rabbits with metastasized squamous carcinoma in the lymph nodes are then used to evaluate the anti‐cancer effects of these particles in the lymph nodes. After percutaneous injection of the particles and upon laser irradiation, through the process of optical droplet vaporization, ultrasound imaging shows a significant increase in contrast in comparison to the control. Histology and electron microscopy confirm damage with disrupted cells throughout the lymph nodes, which slows the tumor growth rate. This study shows that PLGA particles containing PFC liquids can be used as theranostic agents in vivo.     

Synthesis and Optical Properties of KYF4/Yb,Er Nanocrystals,and their Surface Modification with Undoped KYF4

KYF₄/Yb³⁺, Er³⁺ nanocrystals with a mean diameter of approximately 13 nm were synthesized at 200 °C in the high boiling organic solvent N‐(2‐hydroxyethyl)ethylenediamine (HEEDA). The particles crystallize in the cubic phase known from α‐NaYF₄ and form transparent colloidal solutions in tetraethylene glycol (TEG) or propanol. Solutions containing 1 wt % of the nanocrystals in TEG display visible upconversion emission upon continuous wave (CW) excitation at 978 nm. Growing undoped KYF₄ on the surface of the KYF₄/Yb³⁺, Er³⁺ nanocrystals increases the upconversion efficiency by more than a factor of 20. The XRD data of these particles, display a slight increase in the mean particle size from 13 to 15.5 nm, indicating that only a part of the subsequently added KYF₄ shell material is deposited onto the particle surface. Nevertheless the performed surface modification obviously leads to core/shell structured particles.     

Nanoconfined Expansion Behavior of Hollow MnS@Carbon Anode with Extended Lithiation Cyclic Stability

The construction of hollow nanostructure by compositing with carbonaceous materials is generally considered an effective strategy to mitigate the drastic volume expansion of transition metal sulfides (TMSs) with high theoretical specific capacity in the process of lithium storage. However, designing well-controlled architectures with extended lithiation cyclic stability, and ease the expansion of the electroactive materials into the reserved hollow spaces still needs to be developed. Herein, using MnS as an example, the hollow double-shell carbon-coated TMSs architecture is designed to achieve the controllable operation of shell thickness to regulate interfacial stress. The functional architecture enables the high-capacity MnS to reach reversible capacities and extended lithiation cycling stability at high current densities. In situ transmission electron microscopy, optical observation characterizations and finite elements are used to analyze the nanoconfined expansion behavior of hollow MnS@C anodes. The as-designed hollow structure with a carbon shell thickness ≈12.5 nm can effectively restrict the drastic expansion of MnS nanoshell into inner voids with compressive stress. This study demonstrates a general strategy to design functional carbon coating metal sulfides with tailored interfacial stress.     

Magnetochromatic Microcapsule Arrays for Displays

An approach to construct displays based on magnetochromatic microcapsules with narrow size distribution has been proposed. These magnetochromatic microcapsules are fabricated by a microfluidic technology. The shell layer of the obtained microcapsule is composed of transparent photocurable ethoxylated trimethylolpropane triacrylate (ETPTA) resin while the core is formed by the aqueous droplet containing monodisperse magnetic nanospheres. The capsule size, shell thickness, and morphology can be easily controlled by the flow rates during the fabrication. In the multipixel array formed by these microcapsules, each microcapsule acts as an individual display unit. The nanospheres in the core droplet can be influenced by an external magnetic field, forming ordered structures which determine light diffraction; therefore, various distinct colors are observed according to the intensity of the external magnetic field. These microcapsules have the advantage of long time stability, viewing angle independence, and dynamic tunable optics.     

Novel Type‐II InAs/AlSb Core–Shell Nanowires and Their Enhanced Negative Photocurrent for Efficient Photodetection

The control of optical and transport properties of semiconductor heterostructures is crucial for engineering new nanoscale photonic and electrical devices with diverse functions. Core–shell nanowires are evident examples of how tailoring the structure, i.e., the shell layer, plays a key role in the device performance. However, III–V semiconductors bandgap tuning has not yet been fully explored in nanowires. Here, a novel InAs/AlSb core–shell nanowire heterostructure is reported grown by molecular beam epitaxy and its application for room temperature infrared photodetection. The core–shell nanowires are dislocation‐free with small chemical intermixing at the interfaces. They also exhibit remarkable radiative emission efficiency, which is attributed to efficient surface passivation and quantum confinement induced by the shell. A high‐performance core–shell nanowire phototransistor is also demonstrated with negative photoresponse. In comparison with simple InAs nanowire phototransistor, the core–shell nanowire phototransistor has a dark current two orders of magnitude smaller and a sixfold improvement in photocurrent signal‐to‐noise ratio. The main factors for the improved photodetector performance are the surface passivation, the oxide in the AlSb shell and the type‐II bandgap alignment. The study demonstrates the potential of type‐II core–shell nanowires for the next generation of photodetectors on silicon.