Controlling Interface Intermixing and Properties of SrTiO3‐Based Superlattices

By combining state‐of‐the‐art microscopy, spectrosccopy, and first‐principles calculations, atomic‐scale intermixing behavior at heterointerfaces in SrTiO₃‐based superlattices is investigated. It is found that Nb is confined to a unit‐cell thickness without intermixing, whereas Ba diffuses only to the adjoining Nb‐doped SrTiO₃ layer. It is revealed that the intermixing behaviors at the heterointerfaces are determined by not only the migration energy, but also by the vacancy‐formation energy and the Fermi energy of each layer. Based on these results, we find a method to control the atomic‐scale intermixing at the nonpolar heterointerfaces and clearly demonstrate the property improvements obtained by constructing an abrupt heterointerface.     

Hierarchical ZnS‐In2S3‐CuS Nanospheres with Nanoporous Structure: Facile Synthesis,Growth Mechanism,and Excellent Photocatalytic Activity

Without using any templates or surfactants, hierarchical ZnS‐In₂S₃‐CuS nanospheres with nanoporous structure are successfully synthesized via a simple and convenient process. The nanospheres are aggregations of densely packed nanoparticles and nanorods. Different to the oriented attachment (OA) mechanism reported in the literature, the formation of these nanorods is believed to follow a lateral OA mechanism (nanoparticles attach along the direction perpendicular to the crystallographic axes with lateral planes as the juncture) based on the experimental data. This process could be a general phenomenon and would provide a new insight into the OA mechanism. A detailed time‐resolved TEM kinetic study of the formation of the complex structure is shown. The dipole mechanism and electric field‐induced growth are found to be responsible for the final architecture. Photocatalytic activities for water splitting are investigated under visible‐light irradiation (λ > 400 nm) and an especially high photocatalytic activity (apparent yield of 22.6% at 420 nm) is achieved by unloaded ZnIn_0.25Cu_0.02S_1.395 prepared at 180 °C for 18 h because of their high crystallinity, large pore volume, and the presence of nanorods with special microstructures.     

Nanostructured Crystalline Comb Polymer of Perylenebisimide by Directed Self‐Assembly: Poly(4‐vinylpyridine)‐pentadecylphenol Perylenebisimide

Well defined nanostructured polymeric supramolecular assemblies are formed when an asymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3‐pentadecylphenol at the other termini ( PDP‐UPBI ) is complexed with poly(4‐vinylpyridine) (P4VP) via a non‐covalent specific interaction such as hydrogen‐bonding. The resulting P4VP(PDP‐UPBI) _n complexes are fully solution processable. The bulk structure and morphologies of the supramolecular film studied using small angle and wide angle X‐ray scattering reveals highly crystalline nature of the complex. Thin film morphology of the 1:1 complex analyzed using transmission electron microscopy shows uniform lamellar structures in the domain range of 5–10 nm. A clear trend of improved electrical parameters in P4VP(PDP‐UPBI) system compared to pristine ( PDP‐UPBI ) is observed from space charge limited current measurements. In short, a simple and facile method to obtain spatially defined organization of n‐type semiconductor perylenebisimide molecules using hydrogen bonding interactions with P4VP as the structural motif is showcased herein.     

One‐Pot Synthesis of Au25(SG)18 2‐ and 4‐nm Gold Nanoparticles and Comparison of Their Size‐Dependent Properties

A one‐pot synthesis of glutathione (denoted as ‐SG) capped gold nanoparticles, including Au₂₅(SG)₁₈ (ca. 1 nm in diameter) 2‐ and 4‐nm particles is reported. These nanoparticles are isolated by methanol‐induced precipitation with a controlled amount of added methanol. Except for their particle size, these nanoparticles have an identical chemical composition (i.e., gold and ‐SG content), synthetic history, and surface conditions, which allows for precise comparison of their size‐dependent properties, in particular the magnetic property as this could be attributed to contamination by trace iron impurities. Specifically, the structure, optical, and magnetic properties of these gold nanoparticles are compared. A trend from non‐fcc (fcc = face centered cubic) Au₂₅(SG)₁₈ nanoclusters (ca. 1 nm) to 2‐ and 4‐nm fcc‐crystalline Au nanocrystals is revealed. The Au₂₅(SG)₁₈ nanoparticles resemble molecules and exhibit multiple optical absorption peaks ascribed to one‐electron transitions, whereas the 4‐nm nanoparticles exhibit surface plasmon resonance at around 520 nm related to the collective excitation of conduction electrons upon optical excitation. The transition from the non‐fcc cluster state to the fcc crystalline state occurs at around 2 nm. Interestingly, both 2‐ and 4‐nm particles exhibit paramagnetism, whereas the Au₂₅(SG)₁₈ (anionic) clusters are diamagnetic. The information attained on the evolution of the properties of nanoparticles from nanoclusters to fcc‐structured nanocrystals is of major importance and provides insight into structure—property relationships.     

Naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole‐Containing π‐Conjugated Compound: Nonfullerene Electron Acceptor for Organic Photovoltaics

The development of nonfullerene acceptor materials applicable to organic photovoltaics (OPVs) has attracted considerable attention for the achievement of a high power conversion efficiency (PCE) in recent years. However, it is still challenging due to the insufficiency of both the variety of effective electron‐deficient units and certain guidelines for the design of such materials. This work focusses on naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole (NTz) as a key electron‐deficient unit. Therefore, a new electron‐accepting π‐conjugated compound (NTz‐Np), whose structure is based on the combination of NTz and the fluorene‐containing imide‐annelated terminal units (Np), is designed and synthesized. The NTz‐Np compound exhibits a narrow optical energy gap (1.73 eV), a proper energy level (?3.60 eV) of the lowest unoccupied molecular orbital, and moderate electron mobility (1.6 × 10^?5 cm² V^?1 s^?1), indicating that NTz‐Np has appropriate characteristics as an acceptor against poly(3‐hexylthiophene) (P3HT), a representative donor. OPV devices based on NTz‐Np under the blend with P3HT show high photovoltaic performance with a PCE of 2.81%, which is the highest class among the P3HT/nonfullerene‐based OPVs with the conventional device structure. This result indicates that NTz unit can be categorized as a potential electron‐deficient unit for the nonfullerene acceptors.     

α‐Fe2O3 Nanoflakes as an Anode Material for Li‐Ion Batteries

Nanoflakes of α‐Fe₂O₃ were prepared on Cu foil by using a thermal treatment method. The nanoflakes were characterized by X‐ray diffraction, scanning electron microscopy, high‐resolution transmission electron microscopy, and Raman spectroscopy. The reversible Li‐cycling properties of the α‐Fe₂O₃ nanoflakes have been evaluated by cyclic voltammery, galvanostatic discharge–charge cycling, and impedance spectral measurements on cells with Li metal as the counter and reference electrodes, at ambient temperature. Results show that Fe₂O₃ nanoflakes exhibit a stable capacity of (680 ± 20) mA h g^–1, corresponding to (4.05 ± 0.05) moles of Li per mole of Fe₂O₃ with no noticeable capacity fading up to 80 cycles when cycled in the voltage range 0.005–3.0 V at 65 mA g^–1 (0.1 C rate), and with a coulombic efficiency of > 98 % during cycling (after the 15th cycle). The average discharge and charge voltages are 1.2 and 2.1 V, respectively. The observed cyclic voltammograms and impedance spectra have been analyzed and interpreted in terms of the ‘conversion reaction' involving nanophase Fe⁰–Li₂O. The superior performance of Fe₂O₃ nanoflakes is clearly established by a comparison of the results with those for Fe₂O₃ nanoparticles and nanotubes reported in the literature.     

ε‐Branched Flexible Side Chain Substituted Diketopyrrolopyrrole‐Containing Polymers Designed for High Hole and Electron Mobilities

Based on the integrated consideration and engineering of both conjugated backbones and flexible side chains, solution‐processable polymeric semiconductors consisting of a diketopyrrolopyrrole (DPP) backbone and a finely modulated branching side chain (ε‐branched chain) are reported. The subtle change in the branching point from the backbone alters the π?π stacking and the lamellar distances between polymer backbones, which has a significant influence on the charge‐transport properties and in turn the performances of field‐effect transistors (FETs). In addition to their excellent electron mobilities (up to 2.25 cm² V^?1 s^?1), ultra‐high hole mobilities (up to 12.25 cm² V^?1 s^?1) with an on/off ratio (I_on/I_off) of at least 10⁶ are achieved in the FETs fabricated using the polymers. The developed polymers exhibit extraordinarily high electrical performance with both hole and electron mobilities superior to that of unipolar amorphous silicon.     

Charge Disproportionation and Voltage‐Induced Metal–Insulator Transitions Evidenced in β‐PbxV2O5 Nanowires

The roster of materials exhibiting metal–insulator transitions with sharply discontinuous switching of electrical conductivity close to room temperature remains rather sparse, despite the fundamental interest in the electronic instabilities manifested in such materials and the plethora of potential technological applications ranging from frequency‐agile metamaterials to electrochromic coatings and Mott field‐effect transistors. Here, unprecedented, pronounced metal‐insulator transitions induced by application of a voltage are demonstrated for nanowires of a vanadium oxide bronze with intercalated divalent cations, β‐Pb_xV₂O₅ (x ≈ 0.33). The induction of the phase transition through application of an electric field at room temperature makes this system particularly attractive and viable for technological applications. A mechanistic basis for the phase transition is proposed based on charge disproportionation evidenced at room temperature in near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements, ab initio density functional theory calculations of the band structure, and electrical transport data, suggesting that transformation to the metallic state is induced by melting of specific charge localization and ordering motifs extant in these materials.     

Reactive Aramid Nanostructures as High‐Performance Polymeric Building Blocks for Advanced Composites

Traditionally, the field of advanced nanocomposites has relied on a fairly limited set of building blocks; many with low reactivity and of limited variability. These limitations have been addressed by the creation of functionalized nanometer‐scale aramid structures, in the form of nanofibers and nanosheets. These were obtained by deprotonating macroscale, commercial Kevlar yarns using potassium hydroxide in dimethyl sulfoxide to yield stable dispersions of nanometer‐scale aramid fibers that were then hydrolyzed using phosphoric acid (PA). To illustrate the use of these functionally‐active nanostructures as building blocks for nanocomposites, they were crosslinked by glutaraldehyde (GA), and formed into macroscopic thin films by vacuum‐assisted filtration. It was shown that the mechanical properties of these PA/GA treated films can be tuned by varying the amounts of PA and GA used during synthesis, adjusting the relative amounts of hydrolysis and polymerization. These results are the first demonstration that aramid nanometer‐scale fibers can be used to form versatile nanometer‐sized building blocks that can then be crosslinked to fabricate a wide variety of nanostructured aramid materials with tailorable properties.     

A Densely and Uniformly Packed Organic Semiconductor Based on Annelated β‐Trithiophenes for High‐Performance Thin Film Transistors

A novel semiconductor based on annelated β‐trithiophenes is presented, possessing an extraordinary compressed packing mode combining edge‐to‐face π–π interactions and S…S interactions in single crystals, which is favorable for more effective charge transporting. Accordingly, the device incorporating this semiconductor shows remarkably high charge carrier mobility, as high as 0.89 cm² V^?1 s^?1, and an on/off ratio of 4.6 × 10⁷ for vacuum‐deposited thin films.     

Photovoltaic application of O‐doped Wittichenite‐Cu 3 BiS 3: from microscopic properties to maximum efficiencies

The electronic properties and the low environmental impact of Cu ₃ BiS ₃ make this compound a promising material for low‐cost thin film solar cell technology. From the first principles, the electronic properties of the isoelectronic substitution of S by O in Cu ₃ BiS ₃ have been obtained using two different exchange–correlation potentials. This compound has an acceptor level below the conduction band, which modifies the opto‐electronic properties with respect to the host semiconductor. In order to analyze a possible efficiency increment with respect to the host semiconductor, we have calculated the maximum efficiency of this photovoltaic absorber material. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of Optical‐Quality Single‐Crystal β‐BaB2O4 Microwires and Nanowires

The synthesis of optical quality β‐barium borate microwires and nanowires (MNWs) is reported using an organic‐free hydrothermal method with BaCl₂·6H₂O, NaOH, and H₃BO₃ as source materials, and assisted with post‐annealing. As‐synthesized MNWs, with diameters ranging from 500 nm to 2 μm and lengths up to several hundred micrometers, show good optical‐waveguiding capabilities. Based on evanescent coupling between a single BBO MNW waveguide and a fiber taper, propagation losses of 0.30 dB μm^?1 (at 532 nm) and 0.21 dB μm^?1 (at 671 nm) are evaluated, respectively. An evident second‐harmonic generation (SHG) signal at 532 nm with a measured conversion efficiency of about 8.4% is observed when excited by waveguided 1064 nm, picosecond laser pulses within a BBO MNW with a length of the order of 100 μm. The dependence of the SHG conversion efficiency on the MNW diameter is also investigated. These results show a much‐higher SHG efficiency for BBO single‐crystal MNWs compared with bulk crystal, which suggests potential applications in future micro‐/nanoscale nonlinear optical applications such as optical modulation and frequency conversion.     

Stalking the Materials Genome: A Data‐Driven Approach to the Virtual Design of Nanostructured Polymers

Accelerated insertion of nanocomposites into advanced applications is predicated on the ability to perform a priori property predictions on the resulting materials. In this paper, a paradigm for the virtual design of spherical nanoparticle‐filled polymers is demonstrated. A key component of this “Materials Genomics” approach is the development and use of Materials Quantitative Structure‐Property Relationship (MQSPR) models trained on atomic‐level features of nanofiller and polymer constituents and used to predict the polar and dispersive components of their surface energies. Surface energy differences are then correlated with the nanofiller dispersion morphology and filler/matrix interface properties and integrated into a numerical analysis approach that allows the prediction of thermomechanical properties of the spherical nanofilled polymer composites. Systematic experimental studies of silica nanoparticles modified with three different surface chemistries in polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(2‐vinyl pyridine) (P2VP) are used to validate the models. While demonstrated here as effective for the prediction of meso‐scale morphologies and macro‐scale properties under quasi‐equilibrium processing conditions, the protocol has far ranging implications for Virtual Design.     

Alkyl‐Chain‐Length‐Independent Hole Mobility via Morphological Control with Poly(3‐alkylthiophene) Nanofibers

The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO₂ gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.     

Plasmonic Au/TiO2‐Dumbbell‐On‐Film Nanocavities for High‐Efficiency Hot‐Carrier Generation and Extraction

Plasmon‐induced hot carriers have vast potential for light‐triggered high‐efficiency carrier generation and extraction, which can overcome the optical band gap limit of conventional semiconductor‐based optoelectronic devices. Here, it is demonstrated that Au/TiO₂ dumbbell nanostructures assembled on a thin Au film serve as an efficient optical absorber and a hot‐carrier generator in the visible region. Upon excitation of localized surface plasmons in such coupled particle‐on‐film nanocavities, the energetic conduction electrons in Au can be injected over the Au/TiO₂ Schottky barrier and migrated to TiO₂, participating in the chemical reaction occurring at the TiO₂ surface. Compared with the same dumbbell nanostructures on an indium tin oxide (ITO) film, such nanocavities exhibit remarkable enhancement in both photocurrent amplitude and reaction rate that arise from increased light absorption and near‐field amplification in the presence of the Au film. The incident‐wavelength‐dependent photocurrent and reaction rate measurements jointly reveal that Au‐film‐mediated near‐field localization facilitates more efficient electron–hole separation and transport in the dumbbells and also promotes strong d‐band optical transitions in the Au film for generation of extra hot electrons. Such nanocavities provide a new plasmonic platform for effective photoexcitation and extraction of hot carriers and also better understanding of their fundamental science and technological implications in solar energy harvesting.     

Tunable Low‐Field Magnetoresistance in (La0.7Sr0.3MnO3)0.5:(ZnO)0.5 Self‐Assembled Vertically Aligned Nanocomposite Thin Films

Tunable and enhanced low‐field magnetoresistance (LFMR) is observed in epitaxial (La_0.7Sr_0.3MnO₃)_0.5:(ZnO)_0.5 (LSMO:ZnO) self‐assembled vertically aligned nanocomposite (VAN) thin films, which have been grown on SrTiO₃ (001) substrates by pulsed laser deposition (PLD). The enhanced LFMR properties of the VAN films reach values as high as 17.5% at 40 K and 30% at 154 K. They can be attributed to the spin‐polarized tunneling across the artificial vertical grain boundaries (GBs) introduced by the secondary ZnO nanocolumns and the enhancement of spin fluctuation depression at the spin‐disordered phase boundary regions. More interestingly, the vertical residual strain and the LFMR peak position of the VAN films can be systematically tuned by changing the deposition frequency. The tunability of the physical properties is associated with the vertical phase boundaries that change as a function of the deposition frequency. The results suggest that the tunable artificial vertical GB and spin‐disordered phase boundary in the unique VAN system with vertical ferromagnetic‐insulating‐ferromagnetic (FM‐I‐FM) structure provides a viable route to manipulate the low‐field magnetotransport properties in VAN films with favorable epitaxial quality.     

Enhanced Photocatalytic Activity using Layer‐by‐Layer Electrospun Constructs for Water Remediation

Endocrine disruptors such as bisphenol A (BPA) are environmental pollutants that interfere with the body's endocrine system because of their structural similarity to natural and synthetic hormones. Due to their strong oxidizing potential to decompose such organic pollutants, colloidal metal oxide photocatalysts have attracted increasing attention for water detoxification. However, achieving both long‐term physical stability and high efficiency simultaneously with such photocatalytic systems poses many challenges. Here a layer‐by‐layer (LbL) deposition approach is reported for immobilizing TiO₂ nanoparticles (NPs) on a porous support while maintaining a high catalytic efficiency for photochemical decomposition of BPA. Anatase TiO₂ NPs ≈7 nm in diameter self‐assemble in consecutive layers with positively charged polyhedral oligomeric silsesquioxanes on a high surface area, porous electrospun polymer fiber mesh. The TiO₂ LbL nanofibers decompose approximately 2.2 mg BPA per mg of TiO₂ in 40 h of illumination (AM 1.5G illumination), maintaining first‐order kinetics with a rate constant (k) of 0.15 h^?1 for over 40 h. Although the colloidal TiO₂ NPs initially show significantly higher photocatalytic activity (k ≈ 0.84 h^?1), the rate constant drops to k ≈ 0.07 h^?1 after 4 h of operation, seemingly due to particle agglomeration. In the BPA solution treated with the multilayered TiO₂ nanofibers for 40 h, the estrogenic activity, based on human breast cancer cell proliferation, is significantly lower than that in the BPA solution treated with colloidal TiO₂ NPs under the same conditions. This study demonstrates that water‐based, electrostatic LbL deposition effectively immobilizes and stabilizes TiO₂ NPs on electrospun polymer nanofibers for efficient extended photochemical water remediation.     

Recent Developments in One‐Dimensional Inorganic Nanostructures for Photodetectors

With large surface‐to‐volume ratios and Debye length comparable to their small sizes, one‐dimensional inorganic nanostructures have extensively been investigated and widely used to fabricate high‐performance nano­scale electronic and optoelectronic devices. This feature article reviews the state‐of‐the‐art research activities that focus on the one‐dimensional inorganic nanostructures and their photodetector applications. It begins with a survey of one‐dimensional inorganic nanostructures and the fundamentals of photodetectors. Some remarkable photoresponse characteristics are then presented, which are organized into sections covering several kinds of important nanostructures, such as ZnO, V₂O₅, ZnS, In₂Se₃, InSe, CdS, CdSe, ZnSe, Sb₂Se₃, ZrS₂, Ag₂S, and Zn_xCd_1‐xSe. Each section describes the corresponding photodetective properties in detail. Finally, the article concludes with some perspectives and outlook on the future developments in the field.     

Optimized La0.6Sr0.4CoO3–δ Thin‐Film Electrodes with Extremely Fast Oxygen‐Reduction Kinetics

La_0.6Sr_0.4CoO_3–δ (LSC) thin‐film electrodes are prepared on yttria‐stabilized zirconia (YSZ) substrates by pulsed laser deposition at different deposition temperatures. The decrease of the film crystallinity, occurring when the deposition temperature is lowered, is accompanied by a strong increase of the electrochemical oxygen exchange rate of LSC. For more or less X‐ray diffraction (XRD)‐amorphous electrodes deposited between ca. 340 and 510 °C polarization resistances as low as 0.1 Ω cm² can be obtained at 600 °C. Such films also exhibit the best stability of the polarization resistance while electrodes deposited at higher temperatures show a strong and fast degradation of the electrochemical kinetics (thermal deactivation). Possible reasons for this behavior and consequences with respect to the preparation of high‐performance solid oxide fuel cell (SOFC) cathodes are discussed.