Core–Shell Nanoparticles: Characterizing Multifunctional Materials beyond Imaging—Distinguishing and Quantifying Perfect and Broken Shells

Core–shell nanoparticles (NPs) are amongst the most promising candidates in the development of new functional materials. Their fabrication and characterization are challenging, in particular when thin and intact shells are needed. To date no technique has been available that differentiates between intact and broken or cracked shells. Here a method is presented to distinguish and quantify these types of shells in a single cyclic voltammetry experiment by using the different electrochemical reactivities of the core and the shell material. A simple comparison of the charge measured during the stripping of the core material before and after the removal of the shell makes it possible to determine the quality of the shells and to estimate their thickness. As a proof‐of‐concept two multifunctional examples of core–shell NPs, Fe₃O₄@Au and Au@SnO₂, are used. This general and original method can be applied whenever core and shell materials show different redox properties. Because billions of NPs are probed simultaneously and at a low cost, this method is a convenient new screening tool for the development of new multifunctional core–shell materials and is hence a powerful complementary technique or even an alternative to the state‐of‐the‐art characterization of core–shell NPs by TEM.     

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.     

Enhancing the Charge Transport in Solution‐Processed Perylene Di‐imide Transistors via Thermal Annealing of Metastable Disordered Films

The introduction of side chains in π‐conjugated molecules is a design strategy widely exploited to increase molecular solubility thus improving the processability, while directly influencing the self‐assembly and consequently the electrical properties of thin films. Here, a multiscale structural analysis performed by X‐ray diffraction, X‐ray reflectivity, and atomic force microscopy on thin films of dicyanoperylene molecules decorated with either linear or branched side chains is reported. The substitution with asymmetric branched alkyl chains allows obtaining, upon thermal annealing, field‐effect transistors with enhanced transport properties with respect to linear alkyl chains. Branched chains induce molecular disorder during the film growth from solution, effectively favouring 2D morphology. Post‐deposition thermal annealing leads to a structural transition towards the bulk‐phase for molecules with branched chains, still preserving the 2D morphology and allowing efficient charge transport between crystalline domains. Conversely, molecules with linear chains self‐assemble into 3D islands exhibiting the bulk‐phase structure. Upon thermal annealing, these 3D islands keep their size constant and no major changes are observed in the organic field effect transistor characteristics. These findings demonstrate that the disorder generated by the asymmetric branched chains when the molecule is physisorbed in thin film can be instrumental for enhancing charge transport via thermal annealing.     

Facile Fabrication of Highly Dispersed Pd@Ag Core–Shell Nanoparticles Embedded in Spirulina platensis by Electroless Deposition and Their Catalytic Properties

Microorganisms are widely used as the biotemplates for producing micro/nanomaterials owing to their unique features, such as exquisite morphology, renewable, and environmentally friendly. However, mass intracellular synthesis of uniformly dispersed nanoparticles (NPs) inside microorganisms is still challenging, especially in a predictable and controllable manner. Here, a facile and efficiency strategy is proposed to controllably produce highly dispersed and surfactant‐free Pd@Ag core–shell NPs within the Spirulina platensis (Sp.) cells. In this approach, the Sp. cells' permeability is enhanced by the hydrochloric acid treatment first, which enables the Pd NPs penetrate the cell envelope and distribute uniformly inside the cells, and then they can work as the catalytic seeds for the following electroless silver deposition, resulting in the intracellular fabrication of Pd@Ag core–shell NPs with no agglomeration. The Pd@Ag NPs show excellent catalytic activity (turnover frequency is up to 2893 h^?1 for the 6.32 nm Pd@Ag NPs), good stability, and recyclability toward the 4‐nitrophenol reductions. The excellent properties are attributed to the asymmetrical core–shell structure, small size, and good dispersion of Pd@Ag NPs. Due to its facility, cost‐effectiveness, and versatility, this method can be expanded to other microorganisms, so it opens tremendous opportunities for various metallic nanoparticles intracellular synthesis as well as the practical application.     

Reducible‐Shell‐Derived Pure‐Copper‐Nanowire Network and Its Application to Transparent Conducting Electrodes

The concept of using core Cu nanowires (CuNWs) that are conformally encapsulated by a reducible fugitive material for transparent conducting electrodes (TCEs) with high oxidation stability is presented. By the chemical reaction of an acid with surface oxide and hydroxide, a uniform surface shell layer is readily obtained on each CuNW upon adding lactic acid to the CuNW dispersion. The Cu lactate shell prevents the core CuNW from oxidizing during storage and film formation, enabling the core Cu nanowires to maintain their characteristic optoelectronic properties. Through simple thermal annealing under a nitrogen atmosphere, the Cu lactate shell is easily decomposed to expose the underlying pure Cu, providing an effective way to produce a pure‐CuNW‐network TCE with a sheet resistance of 19.8 Ω sq^?1 and an optical transmittance of 85.5% at 550 nm. The application of the CuNW‐based TCE to the transparent top electrode in organometallic halide perovskite solar cells is further demonstrated for the first time, yielding a power‐conversion efficiency 9.88% as compared to that of 13.39% for conventional perovskite solar cells with an indium–tin‐oxide electrode. This study proposes the high feasibility of these CuNWs as a vacuum‐free and noble‐metal‐free transparent‐window electrode in perovskite solar cells.     

Luminescent Core/Shell Nanoparticles with a Rhabdophane LnPO4‐xH2O Structure: Stabilization of Ce3+‐Doped Compositions

The core/shell strategy has been successfully developed for rhabdophane lanthanide phosphate aqueous colloids. The growth of a LaPO₄‐xH₂O shell around Ce,Tb‐doped core nanoparticles increases their stability against oxidation. A bright green luminescence is thus preserved in sol–gel films whose fabrication requires silica coating and thermal treatment of the core/shell nanoparticles.     

A Step‐Wise Approach for Dual Nanoparticle Patterning via Block Copolymer Self‐Assembly

A novel step‐wise approach for fabrication of periodic arrays of two different types of nanoparticles (NPs), selectively localized at different block copolymer phases is demonstrated. In the first step, pre‐synthesized ≈12 nm silver nanoparticles (AgNPs), stabilized with thiol‐terminated polystyrene, are mixed with poly(styrene‐block‐vinylpyridine) (PS‐b‐PVP) block copolymer in a common solvent. After film casting and consequent solvent vapor annealing the AgNPs are selectively localized within the PS phase of the block copolymer matrix due to the interaction with PS shell of the nanoparticles. In the second step, ≈2–5 nm gold, platinum, or palladium nanoparticles are directly deposited from their aqueous dispersion on the PVP domains of the self‐assembled block copolymer thin films. In such a way, thin films of nanostructured block copolymer with two types of nanoparticles, separated by the two distinct block copolymer phases, are prepared in a step‐wise manner. The presented method is very simple and can be applied for various combinations of pre‐synthesized nanoparticles where the characteristics of either type of nanoparticles are tuned accordingly in advance, which is more difficult to achieve for in situ synthesized nanoparticles.     

A Three‐Dimensional Gold‐Decorated Nanoporous Copper Core–Shell Composite for Electrocatalysis and Nonenzymatic Biosensing

Bimetallic core–shell nanostructures have attracted increasing attention due to their low material costs along with enhanced chemico‐physical properties in comparison with their monometallic counterparts. Here, a novel gold‐decorated nanoporous copper (Au@NPC) core–shell composite fabricated by a facile in situ hydrometallurgy approach is reported. Thin gold shells with a controllable thickness are homogeneously deposited onto the internal surfaces of 3D nanoporous copper via a spontaneous displacement reaction while nanoporous copper is utilized as a reduction agent as well as 3D template and substrate. The resulting inexpensive core–shell nanostructure exhibits significant electrocatalytic activity for the oxidation of methanol and high non‐enzymatic sensitivity in detecting glucose.     

Photochemical Formation of Au/Cu Bimetallic Nanoparticles with Different Shapes and Sizes in a Poly(vinyl alcohol) Film

Metal nanoparticle (NP)–polymer nanocomposite thin films are attractive for applications in various devices. Since bimetallic NPs provide additional opportunities for tuning the physical properties of the NP components, the development of bimetallic NP nanocomposite thin films should lead to further enhancements of various applications. Au/Cu bimetallic NPs are fabricated in a poly(vinyl alcohol) (PVA) film using a photochemical process. Interestingly, different sizes and shapes of Au/Cu bimetallic NPs are formed in the PVA film, resulting in a uniquely patterned nanocomposite structure. It is determined that the different formation and growth mechanisms of NPs inside and outside the UV‐light irradiation spot leads to the differences in size and shape.     

Addressing the Reliability and Electron Transport Kinetics in Halide Perovskite Film via Pulsed Laser Engineering

The long‐term performance and stability of perovskites are adversely affected by their porous microstructure, tensile residual stress, and electron transport kinetics. Here, a high‐speed pulsed laser processing technique is implemented to produce beneficial structural changes in organic–inorganic halide perovskites, including pore‐free, crystalline structure, reduced defects, and tensile residual stress. Moreover, halide perovskite films can be converted from p‐type to n‐type semiconductor, which originates from crystal structure changes, giving rise to carrier dynamic changes. Comparing with traditional thermal annealing, residual tensile stress of perovskite thin film decreases by 40% after pulse laser processing, which significantly increases its stability. Pulse‐laser‐induced thermomechanical shock momentum can create pore‐free perovskite thin films, contributing to much better reliability. Under humidity of 80% at room temperature for 500 h, the decomposition rate is reduced by more than two times, comparing thin films after pulsed laser processing with conventional thermal annealing. The thermal decomposition temperature of pulse‐laser‐processed perovskite thin film raises by 20 to about 220 °C. Pulse laser processing technique provides a scalable technique to tailor the structures in perovskite films with both temperature and loading control, further facilitates the design of perovskite‐based devices for service under harsh conditions, and also contributes to high‐performance optoelectronic applications.     

Gold Core‐DNA‐Silver Shell Nanoparticles with Intense Plasmonic Chiroptical Activities

The strong plasmonic chiroptical activities of gold core‐DNA‐silver shell nanoparticles (NPs) are reported for the first time, using cytosine‐rich single‐stranded DNA as the template for the guidance of silver shell growth. The anisotropy factor of the optically active NPs at 420 nm reaches 1.93 × 10^?2. Their chiroptical properties are likely induced by the DNA–plasmon interaction and markedly amplified by the strong electromagnetic coupling between the gold core and silver shell.     

Multifunctional Shell–Core Nanoparticles for Treatment of Multidrug Resistance Hepatocellular Carcinoma

Multidrug resistance (MDR) is the main obstruction against the chemotherapy for hepatocellular carcinoma. Herein, a biodegradable multifunctional tumor‐targeted core–shell structural nanocarrier (RGD peptide functionalized nanoparticles, RGD‐NPs) is reported for treating MDR hepatocellular carcinoma, which consists of three components: pH‐triggered calcium phosphate shell, long circulation phosphatidylserine‐polyethylene glycol (PS‐PEG) core, and an active targeting ligand RGD peptide. Drug‐resistance inhibitor (verapamil, VER) and chemotherapeutic agent (mitoxantrone, MIT) are separately encapsulated into the outer shell layer and inner core layer to obtain VER and MIT loaded RGD‐NPs (VM‐RGD‐NPs). Due to the shell–core structure, the VER and MIT can release sequentially, thus synergistically weakening the efflux effect to MIT by MDR cells. Also, the calcium phosphate can trigger lysosomal escaping through the varied pH value. Together with the optimized internalization pathway in MDR tumor cells, the increased intracellular effective chemotherapeutic drug concentration can be realized, thus achieving the improved curative effect. In this system, the PEG extends the circulation time in vivo. Also, the peptide RGD distinctly increases the affinity to MDR tumors with respect to nontargeted nanoparticles. As a consequence, VM‐RGD‐NPs exhibit a significant synergistic effect toward the MDR hepatocellular carcinoma, providing a promising therapeutic approach for MDR tumor.     

Fluorescence Quenching upon Binding of Copper Ions in Dye‐Doped and Ligand‐Capped Polymer Nanoparticles: A Simple Way to Probe the Dye Accessibility in Nano‐Sized Templates

The synthesis and properties of well‐defined core–shell type fluorescent metal‐chelating polymer nanoparticles NP, in the 15 nm diameter range, with a fluorophore (9,10‐diphenylanthracene: DPA) entrapped in the particle core and a selective ligand (1,4,8,11‐tetraazacyclotetradecane: Cyclam), grafted onto the surface are presented. NPs with different number of dye‐per‐particle are readily obtained by entrapment of the fluorophore within the polymer core. The ligand‐coated NPs exhibit a high affinity for Cu²⁺ ions in aqueous solution and quenching of the DPA fluorescence is observed upon binding of copper. The quenching of fluorescence arises through energy transfer (FRET) from the dye to the copper‐cyclam complexes that form at the NP surface with an operating distance (d) in the 2 nm range. A simple core–shell model accounts for the steady‐state and time‐resolved fluorescence titration experiments: dye molecules located in the outer sphere (thickness d) of the NPs are quenched while the fluorescence of dyes embedded more deeply is not affected by the binding of copper ions. The observed high quenching efficiency (60–65 %), which is tightly correlated to the volumic and microstructural features of the NPs, shed light on the enhanced accessibility inherent in nano‐sized templates. The response towards different metal ions was investigated and this confirmed the selectivity of the nanoparticle template‐assembled sensor for cupric ions.     

Novel Method of Preparation of Gold‐Nanoparticle‐Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell–Garnett Modeling

SiO₂ and TiO₂ thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO₂–Au and TiO₂–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO₂‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO₂ films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.     

A Ligand Exchange Route to Highly Luminescent Surface‐Functionalized ZnS Nanoparticles and Their Transparent Polymer Nanocomposites

A facile ligand exchange approach for surface‐functionalized ZnS nanoparticles (NPs) with 5‐(2‐methacryloylethyloxymethyl)‐8‐quinolinol (MQ) is described. The MQ–ZnS NPs, with a cubic crystal structure, have the same diameter as ZnS NPs without MQ about 3.0 nm. The MQ–ZnS NPs exhibit strong fluorescence emission at about 500 nm and a high photoluminescence (PL) quantum yield (QY), up to 40%, with a decreasing ratio of MQ to ZnS NPs. The PL decay study reveals that the lifetimes of the different MQ–ZnS NPs with a single exponential decay are in the nanosecond time domain for emission at about 500 nm, which is obviously different from that of ZnS NPs with a biexponential decay for defect‐state emission at 420 nm. The functionalized MQ–ZnS NPs are successfully incorporated into the polymer matrix by in situ bulk polymerization to fabricate transparent bulk nanocomposites with good thermal stability and processability. Transmission electron microscopy results show that the NPs are uniformly dispersed in the polymer matrix without aggregation. The good PL properties of MQ–ZnS NPs are preserved in the bulk nanocomposites. It is observed that the nanocomposites have red‐shifted excitation and emission wavelengths compared with those of both the polymer matrix and MQ–ZnS NPs, possibly because of the cooperative interaction between MQ–ZnS NPs and the polymer matrix with blue emission.     

Real‐Time Imaging of Nanoscale Redox Reactions over Bimetallic Nanoparticles

The catalytic performance of bimetallic nanoparticles (NPs) strongly depends on their structural and compositional changes under reaction conditions. At the fundamental level, these changes are driven by redox reactions that occur on the surface of the NPs. The degree of complexity in the redox reactions is further amplified in bimetallic NPs because both metals can have their own reactions with the reactant molecules, in addition to any synergistic effects between the metal nanocatalysts and their reducible oxides. Here, the gas phase oxidation and reduction reactions, and the oxidation of carbon monoxide (CO) over Pt–Ni rhombic dodecahedron NPs with segregated Pt frames and Pt–Ni alloy NPs are investigated using in situ gas cell transmission electron microscopy. The real‐time observations show that NiO shell formation and Pt segregation are two important features during the oxidation and reduction of Pt–Ni NPs, respectively. Moreover, the two types of NPs evolved in different ways. By combining high‐resolution imaging, mass spectroscopy, and modeling, it is shown that the evolution of NP morphology and composition during redox reactions plays an important role in controlling the catalytic activity of the NPs.     

Benzodithiophene Copolymer—A Low‐Temperature,Solution‐Processed High‐Performance Semiconductor for Thin‐Film Transistors

Poly(4,8‐didodecyl‐2,6‐bis‐(3‐methylthiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene) self‐assembled on appropriate substrates from solution and formed highly structured thin films at low temperatures. As an as‐prepared thin‐film semiconductor without thermal annealing, it exhibited excellent field‐effect transistor properties with mobility of ～ 0.15 cm² V^–1 s^–1 in thin‐film transistors.     

Plasmonic‐Assisted Graphene Oxide Films with Enhanced Photothermal Actuation for Soft Robots

Carbon‐based materials are widely used as light‐driven soft actuators relying on their thermal desorption or expansion. However, applying a passive layer in such film construction greatly limits the actuating efficiency, e.g., bending amplitude and speed. In this work, a dual active layer strengthened bilayer composite film made of graphene oxide (GO)–polydopamine (PDA)–gold nanoparticles (Au NPs)/polydimethylsiloxane (PDMS) is developed. In this film, the conventional passive layer is replaced by another AuNPs‐enhanced thermal responsive layer. When applying NIR light exposure, the whole film deforms controllably resulting from the water loss in the GO–PDA–Au NPs layer and thermal expansion in the PDMS layer. Benefiting from the dual active bilayer mechanism, the thin film's actuating efficiency is dramatically improved compared with that of conventional methods. Specifically, the bending amplitude is enhanced up to 173%, and the actuating speed is improved to 3.5‐fold. The soft actuator can act as an artificial arm with high actuating strength and can be used as a wireless gripper. Moreover, the film can be designed as soft robots with various locomotion modes including linear, rolling, and steering motions. The developed composite film offers new opportunities for biomimetic soft robotics as well as future applications.     

Rapid thermal annealing of high-melting-point films onlow-melting-point substrates

Rapid thermal annealing which involves fast heating and cooling rates, is used to activate dopants in thin-film structures yet minimize the dopant diffusion that occurs with excessive thermal exposure. Although the proper resulting electrical properties are the main concern, the structural behavior must also be considered. At the elevated annealing temperature, the heterostructure may be susceptible to both relaxation and yielding. However, the relative effect of these deformations is a function of the material properties, ramp-rate, annealing conditions, and wafer geometry, In particular, for a high-melting-point film on a lower-melting-point substrate, the substrate will experience the inelastic effects prior to the film. More specifically, because germanium has a significantly lower melting point than silicon, previously developed processing technology for silicon cannot be applied directly to germanium processing. A numerical model has been developed to account for the thermo-mechanical effects associated with rapid thermal annealing of relaxing materials. Numerical parametric studies have been conducted for rapid thermal annealing of a thin polysilicon film on a (111) germanium substrate in order to determine the optimum processing window. Results reveal that lower annealing temperatures that still fall within the RTA regime will minimize or even eliminate the plastic damage that could occur during thermal processing     

Self‐Assembly Mechanism of Spiky Magnetoplasmonic Supraparticles

Concave nanoparticles (NPs) with complex angled and non‐Platonic geometries have unique optical, magnetic, catalytic, and biological properties originating from the singularities of the electrical field in apexes and craters. Preparation of such particles with a uniform size/shape and core–shell morphology represents a significant challenge, largely because of the poor knowledge of their formation mechanism. Here, this challenge is addressed and a study of the mechanism of their formation is presented for a case of complex spiky morphologies that led us to the conclusion that NPs with concave geometries can be, in fact, supraparticles (SPs) produced via the self‐assembly of smaller convex integrants. This mechanism is exemplified by the vivid case of spiky SPs formed via the attachment of small and faceted Au NPs on smooth Au‐coated iron oxide (Fe₃O₄@Au) seeds. The theoretical calculations of energies of primary interactions—electrostatic repulsion and van‐der Waals repulsion, elaborated for this complex case—confirm experimental observation and the self‐limiting mechanism of SP formation. Besides demonstrating the mechanistic aspects of synthesis of NPs with complex geometries, this work also uncovers a facile approach for preparation of concave magnetoplasmonic particles. When combined with a spiky geometry, such bi‐functional magnetoplasmonic SPs can serve as a unique platform for optoelectronic devices and biomedical applications.