Alignment of Rod‐Shaped Single‐Photon Emitters Driven by Line Defects in Liquid Crystals

Arrays of liquid crystal defects—linear smectic dislocations—are used to trap semiconductor CdSe/CdS dot‐in‐rods which behave as single‐photon emitters. Measurements of the emission diagram are combined together with measurements of the emitted polarization of the single emitters. It is shown that the dot‐in‐rods are confined parallel to the linear defects to allow for a minimization of the disorder energy associated with the dislocation cores. It is demonstrated that the electric dipoles associated with the dot‐in‐rods, tilted with respect to the rods, remain oriented in the plane including the smectic linear defects and perpendicular to the substrate, most likely due to dipole/dipole interactions between the dipoles of the liquid crystal molecules and those of the dot‐in‐rods. Using smectic dislocations, nanorods can consequently be oriented along a unique direction for a given substrate, independently of the ligands' nature, without any induced aggregation, leading as well to a fixed azimuthal orientation for the dot‐in‐rods' dipoles. These results open the way for the fine control of nanoparticle anisotropic optical properties, in particular, fine control of single‐photon emission polarization.     

Alignment of a Perylene‐Based Ionic Self‐Assembly Complex in Thermotropic and Lyotropic Liquid‐Crystalline Phases

The thermotropic and lyotropic liquid‐crystalline (LC) phases of the ionic self‐assembled complex N,N′,‐bis(2‐(trimethylammonium)ethylene)‐perylene‐3,4,9,10‐tetracarboxyldiimide‐bis(2‐ethylhexyl)sulfosuccinate have been studied using polarizing microscopy, differential scanning calorimetry (DSC), and X‐ray scattering techniques. A two‐dimensional (2D) columnar thermotropic LC phase with π–π stacking of the perylene tectonic units and a lyotropic LC phase in dimethyl sulfoxide (DMSO) have been found. Different techniques have been applied to align both systems and included: surface interactions, electric and magnetic fields, shear force, and controlled domain formation at the LC–isotropic phase‐transition front (PTF). Characterization of the alignment in films has been performed using polarized UV‐vis spectroscopy and transmission null‐ellipsometry. The best results have been obtained for alignment of the material in a lyotropic phase by controlled domain formation at the PTF of the LC–isotropic phase transition. In this case, a dichroic ratio of 18 is achieved with packing of columns of perylenediimide tectons perpendicular to the PTF.     

Controlling the Self‐Assembly of Periodic Defect Patterns in Smectic Liquid Crystal Films with Electric Fields

Large‐area periodic defect patterns are produced in smectic A liquid crystals confined between rigid plate electrodes that impose conflicting parallel and normal anchoring conditions, inducing the formation of topological defects. Highly oriented stripe patterns are created in samples thinner than 2 μm due to self‐assembly of linear defect domains with period smaller than 4 μm, whereas hexagonal lattices of focal conic domains appear for thicker samples. The pattern type (1d/2d) and period can be controlled at the nematic–smectic phase transition by applying an electric field, which confines the defect domains to a thin surface layer with thickness comparable to the nematic coherence length. The pattern morphology persists in the smectic phase even after varying the field or switching it off. Bistable, non‐equilibrium patterns are stabilized by topological constraints of the smectic phase that hinder the rearrangement of defects in response to field variations.     

Exploiting Phonon‐Resonant Near‐Field Interaction for the Nanoscale Investigation of Extended Defects

The evolution of wide bandgap semiconductor materials has led to dramatic improvements for electronic applications at high powers and temperatures. However, the propensity of extended defects provides significant challenges for implementing these materials in commercial electronic and optical applications. While a range of spectroscopic and microscopic tools have been developed for identifying and characterizing these defects, such techniques typically offer either technique exclusively, and/or may be destructive. Scattering‐type scanning near‐field optical microscopy (s‐SNOM) is a nondestructive method capable of simultaneously collecting topographic and spectroscopic information with frequency‐independent nanoscale spatial precision (≈20 nm). Here, how extended defects within 4H‐SiC manifest in the infrared phonon response using s‐SNOM is investigated and the response with UV‐photoluminescence, secondary electron and electron channeling contrast imaging, and transmission electron microscopy is correlated. The s‐SNOM technique identifies evidence of step‐bunching, recombination‐induced stacking faults, and threading screw dislocations, and demonstrates interaction of surface phonon polaritons with extended defects. The results demonstrate that phonon‐enhanced infrared nanospectroscopy and spatial mapping via s‐SNOM provide a complementary, nondestructive technique offering significant insights into extended defects within emerging semiconductor materials and devices and thus serves as an important diagnostic tool to help advance material growth efforts for electronic, photonic, phononic, and quantum optical applications.     

Nematic Anisotropic Liquid‐Crystal Gels—Self‐Assembled Nanocomposites with High Electromechanical Response

The uniqueness of liquid crystals (LCs) lies in the large anisotropies of their properties, which can be utilized to generate high electromechanical responses. In a properly oriented LC polymer system, an external electric field can induce reorientation of the mesogenic units possessing a dielectric anisotropy, which, when coupled with the shape anisotropy of the mesogenic units, can in turn produce large mechanical strain. Anisotropic LC gels, which can be obtained by in‐situ photopolymerization of the reactive LC molecules in the presence of non‐reactive LC molecules in an oriented state, are an example of such liquid‐crystal polymer systems. It is shown here that a homeotropically aligned LC gel in its nematic phase exhibits high electrically induced strain (> 2 %) with an elastic modulus of 100 MPa and a high electromechanical conversion efficiency (75 %) under an electric field of 25 MV/m. These anisotropic LC polymeric materials could provide a technologically compatible system for such applications as artificial muscles and as microelectromechanical devices.     

A prediction of dislocation‐free CdTe/CdS photovoltaic multilayers via nano‐patterning and composition grading

Defects in multilayered films have long been a performance‐limiting problem for the semiconductor industry. For instance, CdTe/CdS solar cell efficiencies have had significant improvement in the past 15years or more without addressing the problem of high misfit dislocation densities. Overcoming this stagnation requires a fundamental understanding of interfacial defect formation. Herein, we demonstrate a new first principles‐based CdTe bond‐order approach that enables efficient molecular dynamics to approach the fidelity of density functional theory. Stringent quantum‐mechanical verification and experimental validation tests reveal that our new approach provides an accurate prediction of defects that earlier methods cannot. Using this new capability, we show that misfit dislocations in CdTe/CdS multilayers can be significantly reduced via nano‐patterning and composition grading and more importantly, dislocation‐free multilayers naturally arise when the pattern dimension is reduced below 90nm. Our predictive methods are generally applicable to other materials, highlighting a rational approach towards low‐defect semiconductor films. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of Electric Field on Microstructures of Pentacene Thin‐Films in Field‐Effect Transistors

We report on electric‐field‐induced irreversible structural modifications in pentacene thin films after long‐term operation of organic field‐effect transistor (OFET) devices. Micro‐Raman spectroscopy allows for the analysis of the microstructural modifications of pentacene in the small active channel of OFET during device operation. The results suggest that the herringbone packing of pentacene molecules in a solid film is affected by an external electric field, particularly the source‐to‐drain field that parallels the a–b lattice plane. The analysis of vibrational frequency and Davydov splitting in the Raman spectra reveals a singular behavior suggesting a reduced separation distance between pentacene molecules after long‐term operations and, thus, large intermolecular interactions. These results provide evidence for improved OFET performance after long‐term operation, related to the microstructures of organic semiconductors. It is known that the application of large electric fields alters the semiconductor properties of the material owing to the generation of defects and the trapping of charges. However, we first suggest that large electric fields may alter the molecular geometry and further induce structural phase transitions in the pentacene films. These results provide a basis for understanding the improved electronic properties in test devices after long‐term operations, including enhanced field‐effect mobility, improved on/off current ratio, sharp sub‐threshold swing, and a slower decay rate in the output drain current. In addition, the effects of source‐to‐drain electric field, gate electric field, current and charge carriers, and thermal annealing on the pentacene films during OFET operations are discussed.     

Enhanced Collective Magnetic Properties Induced by the Controlled Assembly of Iron Oxide Nanoparticles in Chains

1D assemblies of magnetic nanoparticles are of great potential for designing novel nanostructured materials with enhanced collective magnetic properties. In that challenging context, a new assembly strategy is presented to prepare chains of magnetic nanoparticles that are well‐defined in structure and in spatial arrangement. The 1D assembly of iron oxide nanoparticles onto a substrate is controlled using “click” chemistry under an external magnetic field. Co‐aligned single nanoparticle chains separated by regular distances can be obtained by this strategy. The intrinsic high uniaxial anisotropy results in a strong enhancement of magnetic collective properties in comparison to 2D monolayers or isolated nanoparticles. In contrast to the intensively studied bundle chains of nanoparticles, the finely tuned chain structure reported here allows evidencing a first order intrachain dipolar interaction and a second order interchain magnetic coupling. This study offers new insights into the collective magnetic properties of highly anisotropic particulate assemblies which have been investigated by combining superconducting quantum interference device magnetometry, magnetic force microscopy, and ferromagnetic resonance.     

Preparation and Organization of Nanoscale Polyelectrolyte‐Coated Gold Nanoparticles

The layer‐by‐layer (LbL) desposition of oppositely charged polyelectrolytes from adsorption solutions of different ionic strength onto ～7 nm diameter carboxylic acid‐derivatized gold nanoparticles has been studied. The polyelectrolyte‐modified nanoparticles were characterized by UV‐vis spectrophotometry, microelectrophoresis, analytical ultracentrifugation, and transmission electron microscopy. UV‐vis data showed that the peak plasmon absorption wavelength of the gold nanoparticles red‐shifted after each adsorption step, and microelectrophoresis experiments revealed a reversal in the surface charge of the nanoparticles following deposition of each layer. These data are consistent with the formation of polyelectrolyte layers on the nanoparticles. Analytical ultracentrifugation showed an increase in mean nanoparticle diameter on adsorption of the polyelectrolytes, confirming the formation of gold‐core/polyelectrolyte‐shell nanoparticles. Transmission electron microscopy studies showed no signs of aggregation of the polyelectrolyte‐coated nanoparticles. The adsorption of the polyelectrolyte‐coated gold nanoparticles onto oppositely charged planar supports has also been examined. UV‐vis spectrophotometry and atomic force microscopy showed increased amounts of nanoparticles were adsorbed with increasing ionic strength of the nanoparticle dispersions. This allows control of the nanoparticle surface loading by varying the salt content in the nanoparticle dispersions used for adsorption. The LbL strategy used in this work is expected to be applicable to other nanoparticles (e.g., semiconductors, phosphors), thus providing a facile means for their controlled surface modification through polyelectrolyte nanolayering. Such nanoparticles are envisaged to have applications in the biomedical and bioanalytical fields, and to be useful building blocks for the creation of advanced nanoparticle‐based films.     

CdTe/CdS、CdTe/ZnS核壳结构半导体量子点制备及荧光特性

核壳半导体量子点材料因其在修复单量子点表面缺陷方面的特殊性能,极大地提高了量子点的光学性能而受到人们的研究。改进了CdTe核心的制作方法,使用小型三口瓶替代传统的小烧瓶作为反应容器,制备碲氢化钠,合成了不同核心尺寸、不同壳层厚度与不同壳层材料的10种CdTe/CdS、CdTe/ZnS核壳结构半导体量子点。对10种核壳结构半导体量子点材料进行紫外可见吸收光谱及荧光光谱测试,并分析其荧光特性。量子点在紫外可见波段的吸收光谱表明随着量子点尺寸的增大,吸收峰发生红移。通过实验结果与分析可推断出CdTe/CdS量子点荧光寿命和强度的不同是由于核心和壳层尺寸的不同量子点在I型和II型中相互转换;CdTe/ZnS的壳层厚度增加时,由于ZnS的壳层降低了核心外表的悬空键和表面缺陷态的数量,使电子空穴对复合机率加大,使得荧光峰位产生了红移。     

The Active‐Core/Active‐Shell Approach: A Strategy to Enhance the Upconversion Luminescence in Lanthanide‐Doped Nanoparticles

Nanoparticles of NaGdF₄ doped with trivalent erbium (Er³⁺) and ytterbium (Yb³⁺) are prepared by a modified thermal decomposition synthesis from trifluoroacetate precursors in 1‐octadecene and oleic acid. The nanoparticles emit visible upconverted luminescence on excitation with near‐infrared light. To minimize quenching of this luminescence by surface defects and surface‐associated ligands, the nanoparticles are coated with a shell of NaGdF₄. The intensity of the upconversion luminescence is compared for nanoparticles that were coated with an undoped shell (inert shell) and similar particles coated with a Yb³⁺‐doped shell (active shell). Luminescence is also measured for nanoparticles lacking the shell (core only), and doped with Yb³⁺ at levels corresponding to the doped and undoped core/shell materials respectively. Upconversion luminescence was more intense for the core/shell materials than for the uncoated nanoparticles, and is greatest for the materials having the “active” doped shell. Increasing the Yb³⁺ concentration in the “core‐only” nanoparticles decreases the upconversion luminescence intensity. The processes responsible for the upconversion are presented and the potential advantages of “active‐core”/“active‐shell” nanoparticles are discussed.     

Mn2+‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Recent advances in the chemistry of colloidal semiconductor nanocrystal doping have led to new materials showing fascinating physical properties of potential technological importance. This article provides an overview of efforts to dope one of the most widely studied colloidal semiconductor nanocrystal systems, CdSe quantum dots, with one of the most widely studied transition‐metal dopant ions, Mn²⁺, and describes the major new physical properties that have emerged following successful synthesis of this material. These properties include spin‐polarizable excitonic photoluminescence, magnetic circular dichroism, exciton storage, and excitonic magnetic polaron formation. A brief survey of parallel advances in the characterization of analogous self‐assembled Mn²⁺‐doped quantum dots grown by molecular beam epitaxy is also presented, and the physical properties of the colloidal quantum dots are shown to compare favorably with those of the self‐assembled quantum dots. The rich variety of physical properties displayed by colloidal Mn²⁺‐doped CdSe quantum dots highlights the attractiveness of this material for future fundamental and applied research.     

Electric Field‐Directed Convective Assembly of Ellipsoidal Colloidal Particles to Create Optically and Mechanically Anisotropic Thin Films

A method of simultaneous field‐ and flow‐directed assembly of anisotropic titania (TiO₂) nanoparticle films from a colloidal suspension is presented. Titania particles are oriented by an alternating (ac) electric field as they simultaneously advect towards a drying front due to evaporation of the solvent. At high field frequencies (ν > ～25 kHz) and field strengths (E > 300 V cm^?1), the particles orient with their major axis along the field direction. As the front recedes, a uniform film with thicknesses of 1–10 µm is deposited on the substrate. The films exhibit a large birefringence (Δn ≈ 0.15) and high packing fraction (? = 0.75 ± 0.08), due to the orientation of the particles. When the frequency is lowered, the particle orientation undergoes a parallel–random–perpendicular transition with respect to the field direction. The orientation dependence on field frequency and strength is explained by the polarizability of ellipsoidal particles using an interfacial polarization model. Particle orientation in the films also leads to anisotropic mechanical properties, which are manifested in their cracking patterns. In all, it is demonstrated that the field‐directed assembly of anisotropic particles provides a powerful means for tailoring nanoparticle film properties in situ during the deposition process.     

Smectic Liquid Crystal Defects for Self‐Assembling of Building Blocks and Their Lithographic Applications

Recently, it has been reported that liquid crystal (LC) defects can be used to create highly periodic templates by controlling the surface anchoring and the elastic properties of LC molecules. The self‐assembled defect ordering of the LC materials takes advantage of the ability to achieve fast stabilization of molecular ordering and structure due to the reversible and non‐covalent interactions of the LC molecules. In this Featre Article, the defect structures of liquid crystalline materials will be demonstrated by the surface anchoring and elastic properties. A particular focus are the focal conic domains (FCDs) that are commonly observed in SmA liquid crystals and their lamellar lyotropic counterparts, which form periodic defect ordered structures. In addition, methodologies for creating lithographic templates from the defect order will be described. Finally, the review closes with a discussion of toric focal conic domain arrays that have been fabricated in this manner and used for various applications.     

Electrically Directed On‐Chip Reversible Patterning of Two‐Dimensional Tunable Colloidal Structures

In this work, we report a versatile approach to two‐dimensional colloidal patterning based on the lateral assembly of colloidal particles by an alternating electric field (AEF). Under the AEF, the lithographically templated electrodes provide an effective way to reversibly and rapidly assemble colloidal particles into some desirable patterns. By controlling the AEF and the electrode pattern geometry, various colloidal patterns with tunable lattice spacing and even with binary lattice spacing have been formed. Particularly, we demonstrate that well‐defined linear defects can be embedded inside the colloidal crystals, whereas the unwanted existing defects can be controllably relaxed by this patterning process. This novel patterning technique is amenable to both large scale on‐chip patterning and micro‐structural control with single‐particle resolution on a time scale of seconds. Furthermore, it introduces a new class of colloidal structures with the properties that can be finely tuned, reversibly switched, or permanently fixed, opening a new way for the engineering of novel materials and devices at micro levels.     

Biospecific Self‐Assembly of a Nanoparticle Coating for Targeted and Stimuli‐Responsive Drug Delivery

Biology provides a range of materials, mechanisms, and insights to meet the diverse requirements of nanomedicine. Here, a biologically based nanoparticle coating system that offers three characteristic features is reported. First, the coating can be self‐assembled through a noncovalent biospecific interaction mechanism between a lectin protein (Concanavalin A) and the polysaccharide glycogen. This biospecific self‐assembly enables the coating to be applied simply without the generation of covalent bonds. Second, glycoprotein‐based biofunctionality can be incorporated into the coating through the same noncovalent biospecific interaction mechanism. Here, the glycoprotein transferrin is incorporated into the coating since this moiety is commonly used to target cancer cells through a receptor‐mediated endocytosis mechanism. Third, the coating can be triggered to disassemble in response to a reduction in pH that is characteristic of endosomal uptake. In a proof‐of‐concept study, comparing coated and uncoated nanoparticles, model drug‐loaded nanoparticles (doxorubicin‐loaded mesoporous silica nanoparticles) are prepared and it is observed that the coated nanoparticle has enhanced cytotoxicity for cancer cell lines but attenuated cytotoxicity for noncancerous cell lines. These studies demonstrate that biology provides unique materials and mechanism appropriate to meet the needs for emerging applications in the medical and life sciences.     

Microfluidic Fabrication of Capsule Sensor Platform with Double‐Shell Structure

Metal nanoparticles are frequently employed for the colorimetric detection of specific target molecules using an aggregation‐induced shift of the localized surface plasmon resonance. However, metal nanoparticles dispersed in bulk solutions are prone to be contaminated by adhesive molecules and the dispersions tend to be diluted by sample fluids, restricting direct application to unpurified pristine samples. Here, a versatile capsule sensor platform is proposed that can encompass a variety of different types of nanoparticle‐based sensors. The capsule sensors are microfluidically prepared to obtain close control over their dimensions and composition. Their aqueous cores that are loaded with sensing materials are surrounded by an ultrathin inner oil shell and an outer hydrogel shell. The hydrogel shell prevents the diffusion of large adhesive molecules into the core, thereby preventing contamination of the sensing materials. The oil shell is selectively permeable such that it further improves the sensor selectivity. Importantly, these shells confine the sensing materials and prevent them from being diluted, securing a consistent optical property. Moreover, the capsule‐based sensors display a higher sensitivity than bulk dispersions because a smaller amount of sensing materials is used. The power of nanoparticle‐loaded capsule sensors is demonstrated using lysine‐coated gold nanoparticles to detect mercury ions.     

Photoreplicated Anisotropic Liquid‐Crystalline Lenses for Aberration Control and Dual‐Layer Readout of Optical Discs

This work describes the functional characterization of novel photoreplicated anisotropic lenses obtained from molds with different curvatures. These lenses were prepared by the photopolymerization of mixtures of a reactive liquid‐crystalline bisacrylate and non‐reactive derivatives of liquid‐crystalline cyanobiphenyl. The phase diagrams, the polymerization kinetics as a function of temperature, and the birefringence as a function of temperature for various mixtures were determined. For the fabrication of lenses, the average liquid‐crystal (LC) director of the mixtures has to be aligned in a single direction. Photoalignment and rubbing techniques were investigated to create a monodomain of the reactive material. Finally, optimal mixtures were used for the fabrication of anisotropic lenses. Aberrations were below 20 mλ root mean square (rms), which makes these LC lenses interesting for application in light paths, for example, as spherical aberration correction devices for dual‐ (or multiple‐) layer optical storage.     

Design and Synthesis of “All‐in‐One” Multifunctional FeS2 Nanoparticles for Magnetic Resonance and Near‐Infrared Imaging Guided Photothermal Therapy of Tumors

The ideal theranostic nanoplatform for tumors is a single nanoparticle that has a single semiconductor or metal component and contains all multimodel imaging and therapy abilities. The design and preparation of such a nanoparticle remains a serious challenge. Here, with FeS₂ as a model of a semiconductor, the tuning of vacancy concentrations for obtaining “all‐in‐one” type FeS₂ nanoparticles is reported. FeS₂ nanoparticles with size of ≈30 nm have decreased photoabsorption intensity from the visible to near‐infrared (NIR) region, due to a low S vacancy concentration. By tuning their shape/size and then enhancing the S vacancy concentration, the photoabsorption intensity of FeS₂ nanoparticles with size of ≈350 nm (FeS₂‐350) goes up with the increase of the wavelength from 550 to 950 nm, conferring the high NIR photothermal effect for thermal imaging. Furthermore, this nanoparticle has excellent magnetic properties for T₂‐weighted magnetic resonance imaging (MRI). Subsequently, FeS₂‐350 phosphate buffer saline (PBS) dispersion is injected into the tumor‐bearing mice. Under the irradiation of 915‐nm laser, the tumor can be ablated and the metastasis lesions in liver suffer significant inhibition. Therefore, FeS₂‐350 has great potential to be used as novel “all‐in‐one” multifunctional theranostic nanoagents for MRI and NIR dual‐modal imaging guided NIR‐photothermal ablation therapy (PAT) of tumors.     

Chiral 2D Colloidal Semiconductor Quantum Wells

Induced chirality in colloidal semiconductor nanoparticles has raised significant attention in the past few years as an extremely sensitive spectroscopic tool and due to the promising applications of chiral quantum dots in sensing, quantum optics, and spintronics. Yet, the origin of the induced chiroptical effects in semiconductor nanoparticles is still not fully understood, partly because almost all the theoretical and experimental studies to date are based on the simple model system of a spherical nanocrystal. Here, the realization of induced chirality in atomically flat 2D colloidal quantum wells is shown. A strong circular dichroism (CD) response as well as an absorptive‐like CD line shape is observed in chiral CdSe nanoplatelets (NPLs), significantly differing from that previously observed in spherical dots. Furthermore, this intense CD signal almost completely disappears after coating with a very thin CdS shell. In contrast, CdSe‐CdS core‐crown NPLs exhibit a spectral response which seems to originate independently from the core and the crown regions of the NPL. This work on the one hand further advances the understanding of the fundamental origin of induced chiroptical effects in semiconductor nanoparticles, and on the other opens a pathway toward applications using chiroptical materials.