Topology Optimization‐Based Inverse Design of Plasmonic Nanodimer with Maximum Near‐Field Enhancement

The near‐field enhancement factor is one of the most significant parameters to evaluate the performance of plasmonic nanostructures. Numerous efforts have been made to maximize the enhancement factor through optimizing the size, shape, and spatial arrangement of metallic nanostructures with simple geometries, such as disk, triangle, and rod. This work implements topology optimization to inversely design a metallic nanoparticle dimer with the goal of optimizing the near‐field enhancement factor in its sub‐10 nm gap. By optimizing the material layout within a given design space, the topology optimization algorithm results in a plasmonic nanodimer of two heart‐shaped particles having both convex and concave features. Full‐wave electromagnetic analysis reveals that the largest near‐field enhancement in the heart‐shaped nanoparticle dimer is originated from the greatest concentration of surface charges at the nano‐heart apex. Inversely designed heart‐, bowtie‐, and disk‐shaped nanodimers are fabricated by using focused helium ion beam milling with a “sketch and peel” strategy, and their near‐field enhancement performances are characterized with nonlinear optical spectroscopies at the single‐particle level. Indeed, the heart‐shaped nanodimer exhibits much stronger signal intensities than the other two structures. The present work corroborates the validity and effectiveness of topology optimization‐based inverse design in achieving desired plasmonic functionalities.     

Electrosynthesis of NbTi and Nb3Sn Superconductors from Oxide Precursors in CaCl2‐Based Melts

NbTi and Nb₃Sn superconductors have been synthesized directly from the oxides by electro‐deoxidation, where the cathode is made by placing an intimate mixture of the sintered oxide in a molten bath of calcium chloride and sodium chloride. The favored cathodic reaction is the removal of the oxygen from the oxides to form the superconducting intermetallic alloys and not the deposition of calcium. The superconducting properties of the intermetallic compounds are confirmed.     

艾里(Airy)光束的零场截取和变换性质

本文用数值模拟证明 Airy光束或 Airy斑 (Airy Pattern)经零场截取后 ,其中央亮斑或 Airy芯(Airy disc)甚至在远场也不会产生新的衍射旁瓣 (在 10 - 3～ 10 - - 6 以下 )。尔后 ,举例分析了它独特的变换性质。     

A Semi‐Floating Memory with 535% Enhancement of Refresh Time by Local Field Modulation

The recently proposed semi‐floating gate memory technology shows the potential to balance conflicts between writing speed and data storage. Although the introduction of the p–n junction greatly improves device writing speed, the inevitable junction leakage limits the further extension of data retention time. A local nonvolatile electric field is introduced by exploiting the polarization of ferroelectric gate dielectric HfZrO₄ to modulate the charge leakage speed of the p–n junction since the carrier density of 2D materials can be efficiently regulated. The refresh time is greatly prolonged more than 535%, solving the bottleneck problem of relatively short retention time of previous semi‐floating gate memory. In addition, the characteristics of device under low operation voltage is also explored, which can serve for further power reducing. This design realizes the combination of ultrafast writing operation and significant enhanced data retention ability, which provides a new idea of the development for high speed non‐volatile memory technology.     

Long‐Range Nonvolatile Electric Field Effect in Epitaxial Fe/Pb(Mg1/3Nb2/3)0.7Ti0.3O3 Heterostructures

One of the ideal candidates of using electric field to manipulate magnetism is the recently developed multiferroics with emergent coupling of magnetism and electricity, particularly in synthesizing artificial nanoscale ferroelectric and ferromagnetic materials. Here, a long‐range nonvolatile electric field effect is investigated in Fe/Pb(Mg_1/3Nb_2/3)_0.7Ti_0.3O₃ heterostructure using the dependence of the magnon‐driven magnetoelectric coupling on the epitaxial Fe thin film (4–30 nm) thickness at room temperature using measurements based on the ferromagnetic resonance. The magnon‐driven magnetoelectric coupling tuning of the ferromagnetic resonance field shows a linear response to the electric field, with a resonance field shift that occurs under both positive and negative remanent polarizations, and demonstrates nonvolatile behavior. Moreover, the spin diffusion length of the epitaxial Fe thin film of ≈9 nm is obtained from the results that the change of the cubic magnetocrystalline anisotropy field under different electric fields varies with Fe thickness. These results are promising for the design of future multiferroic devices.     

Planarization of Polymeric Field‐Effect Transistors: Improvement of Nanomorphology and Enhancement of Electrical Performance

The planarization of bottom‐contact organic field‐effect transistors (OFETs) resulting in dramatic improvement in the nanomorphology and an associated enhancement in charge injection and transport is reported. Planar OFETs based on regioregular poly(3‐hexylthiophene) (rr‐P3HT) are fabricated wherein the Au bottom‐contacts are recessed completely in the gate‐dielectric. Normal OFETs having a conventional bottom‐contact configuration with 50‐nm‐high contacts are used for comparison purpose. A modified solvent‐assisted drop‐casting process is utilized to form extremely thin rr‐P3HT films. This process is critical for direct visualization of the effect of planarization on the polymer morphology. Atomic force micrographs (AFM) show that in a normal OFET the step between the surface of the contacts and the gate dielectric disrupts the self‐assembly of the rr‐P3HT film, resulting in poor morphology at the contact edges. The planarization of contacts results in notable improvement of the nanomorphology of rr‐P3HT, resulting in lower resistance to charge injection. However, an improvement in field‐effect mobility is observed only at short channel lengths. AFM shows the presence of well‐ordered nanofibrils extending over short channel lengths. At longer channel lengths the presence of grain boundaries significantly minimizes the effect of improvement in contact geometry as the charge transport becomes channel‐limited.     

Tuning Contact Resistance in Top‐Contact p‐Type and n‐Type Organic Field Effect Transistors by Self‐Generated Interlayers

Contact resistance significantly limits the performance of organic field‐effect transistors (OFETs). Positioning interlayers at the metal/organic interface can tune the effective work‐function and reduce contact resistance. Myriad techniques offer interlayer processing onto the metal pads in bottom‐contact OFETs. However, most methods are not suitable for deposition on organic films and incompatible with top‐contact OFET architectures. Here, a simple and versatile methodology is demonstrated for interlayer processing in both p‐ and n‐type devices that is also suitable for top‐contact OFETs. In this approach, judiciously selected interlayer molecules are co‐deposited as additives in the semiconducting polymer active layer. During top contact deposition, the additive molecules migrate from within the bulk film to the organic/metal interface due to additive‐metal interactions. Migration continues until a thin continuous interlayer is completed. Formation of the interlayer is confirmed by X‐ray photoelectron spectroscopy (XPS) and cross‐section scanning transmission electron microscopy (STEM), and its effect on contact resistance by device measurements and transfer line method (TLM) analysis. It is shown that self‐generated interlayers that reduce contact resistance in p‐type devices, increase that of n‐type devices, and vice versa, confirming the role of additives as interlayer materials that modulate the effective work‐function of the organic/metal interface.     

Critical Aspects and Recent Advances in Structural Engineering of Photocatalysts for Sunlight‐Driven Photocatalytic Reduction of CO2 into Fuels

The catalytic conversion of CO₂ into valuable fuels is a compelling solution for tackling the global warming and fuel crisis. Light absorption and charge separation, as well as adsorption/activation of CO₂ on the photocatalyst surface, are essential steps for this process. This article reviews the CO₂ photoreduction mechanisms and critical aspects that greatly affect the photoreduction efficiency. Additionally, different materials for CO₂ photoreduction are provided, including d⁰ and d¹⁰ metal oxides/mixed oxides, sulfides, polymeric materials, and metal phosphides with visible response, metal‐organic frameworks, and layer double hydroxides. Furthermore, various structural engineering strategies and corresponding state‐of‐the‐art photocatalytic systems are reviewed and discussed, such as bandgap engineering, geometrical nanostructure engineering, and heterostructure engineering. Each strategy has advantages and disadvantages, requiring further adjustment to further improve the photocatalytic performance of the photocatalyst. Based on this review, it is greatly expected that efficiently artificial systems and the breakthrough technologies for CO₂ reduction will be successfully developed in the future to solve the energy shortage as well as the environmental problem.     

Analysis of Failure in Miniature X‐ray Tubes with Gated Carbon Nanotube Field Emitters

We correlate the failure in miniature X‐ray tubes with the field emission gate leakage current of gated carbon nanotube emitters. The miniature X‐ray tube, even with a small gate leakage current, exhibits an induced voltage on the gate electrode by the anode bias voltage, resulting in a very unstable operation and finally a failure. The induced gate voltage is apparently caused by charging at the insulating spacer of the miniature X‐ray tube through the gate leakage current of the field emission. The gate leakage current could be a criterion for the successful fabrication of miniature X‐ray tubes.     

Structural and Spectroscopic Characterization of Nominal Yb3+:Ca8La2(PO4)6O2 Oxyapatite Single Crystal Fibers Grown by the Micro‐Pulling‐Down Method

Yb‐doped Ca₈La₂(PO₄)₆O₂ (CLPA) single crystals with the apatite‐type structure and having <0001> orientation were grown by the micro‐pulling‐down (μ‐PD) method. The apatite structure is represented by the monophased field of Ca₈(La_2–xYb_x)‐(PO₄)₆O₂ (CLYPA) where it is assumed that 2 Ca²⁺ sites are substituted by La³⁺ and Yb³⁺ cations. Its monophased range was found to be from x = 0.0 to 0.2. The segregation of Yb³⁺ in CLPA single crystals and the maximum Yb³⁺ concentration are discussed. The crystallinity was studied using X‐ray rocking curve analysis. Absorption, emission and fluorescence decay studies of Yb³⁺ ions in CLPA were also carried out both at low temperature and room temperature. Spectroscopic data reveal Yb³⁺ ion occupation within different crystallographic sites of the apatite‐type structure. The potential for a diode‐pumped Yb³⁺ laser is evaluated.     

One‐Step Self‐Assembly Fabrication of High Quality NixMg1‐xO Bowl‐Shaped Array Film and Its Enhanced Photocurrent by Mg,2+ Doping

A series of high quality Ni_xMg_1‐xO bowl‐shaped array films are successfully prepared by a simple one‐step assembly of polystyrene colloidal spheres and metal oxide precursors at oil–water interface, and further used to fabricate nanodevices. The doping of Mg²⁺ can greatly enhance the current and spectrum responsivity of NiO film‐based nanodevice. The maximum R_λ value of these bowl‐shaped Ni_xMg_1‐xO film‐based devices measured in the study shows 4–5 orders of enhancement than the previously reported Ni_xMg_1‐xO film at equal doping.     

High‐Resolution Near‐Field Optical Investigation of Crystalline Domains in Oligomeric PQT‐12 Thin Films

The structure and morphology on different length scales dictate both the electrical and optical properties of organic semiconductor thin films. Using a combination of spectroscopic methods, including scanning near‐field optical microscopy, we study the domain structure and packing quality of highly crystalline thin films of oligomeric PQT‐12 with 100 nanometer spatial resolution. The pronounced optical anisotropy of these layers measured by polarized light microscopy facilitates the identification of regions with uniform molecular orientation. We find that a hierarchical order on three different length scales exists in these layers, made up of distinct well‐ordered dichroic areas at the ten‐micrometer‐scale, which are sub‐divided into domains with different molecular in‐plane orientation. These serve as a template for the formation of smaller needle‐like crystallites at the layer surface. A high degree of crystalline order is believed to be the cause of the rather high field‐effect mobility of these layers of 10^?3 cm² V^?1 s^?1, whereas it is limited by the presence of domain boundaries at macroscopic distances.     

Enhancement of Interconnectivity in the Channels of Pentacene Thin‐Film Transistors and Its Effect on Field‐Effect Mobility

With the aim of improving the field‐effect mobility of transistors by promoting the interconnectivity of the grains in pentacene thin films, deposition conditions of the pentacene molecules using one‐step (total thickness of layer 50 nm: 0.1 Å s^–1) and two‐step (first layer 10 nm: 0.1 Å s^–1, second layer 40 nm: 4.0 Å s^–1) depositions are controlled. Significantly, it is found that the continuities of the pentacene thin films vary with the deposition conditions of the pentacene molecules. Specifically, a smaller number of voids is observed at the interface for the two‐step deposition, which results in field‐effect mobilities as high as 1.2 cm² V^–1 s^–1; these are higher by more than a factor of two than those of the pentacene films deposited in one step. This remarkable increase in field‐effect mobility is due in particular to the interconnectivity of the pentacene grains near the insulator substrate.     

Angular‐Shaped 4,9‐Dialkyl α‐ and β‐Naphthodithiophene‐Based Donor–Acceptor Copolymers: Investigation of Isomeric Structural Effects on Molecular Properties and Performance of Field‐Effect Transistors and Photovoltaics

Two angular‐shaped 4,9‐didodecyl α‐aNDT and 4,9‐didodecyl β‐aNDT isomeric structures have been regiospecifically designed and synthesized. The distannylated α‐aNDT and β‐aNDT monomers are copolymerized with the Br‐DTNT monomer by the Stille coupling to furnish two isomeric copolymers, PαNDTDTNT and PβNDTDTNT, respectively. The geometric shape and coplanarity of the isomeric α‐aNDT and β‐aNDT segments in the polymers play a decisive role in determining their macroscopic device performance. Theoretical calculations show that PαNDTDTNT possesses more linear polymeric backbone and higher coplanarity than PβNDTDTNT. The less curved conjugated main chain facilitates stronger intermolecular π–π interactions, resulting in more redshifted absorption spectra of PαNDTDTNT in both solution and thin film compared to the PβNDTDTNT counterpart. 2D wide‐angle X‐ray diffraction analysis reveals that PαNDTDTNT has more ordered π‐stacking and lamellar stacking than PβNDTDTNT as a result of the lesser curvature of the PαNDTDTNT backbone. Consistently, PαNDTDTNT exhibits a greater field effect transistor hole mobility of 0.214 cm² V^?1 s^?1 than PβNDTDTNT with a mobility of 0.038 cm² V^?1 s^?1. More significantly, the solar cell device incorporating the PαNDTDTNT:PC₇₁BM blend delivers a superior power conversion efficiency (PCE) of 8.01% that outperforms the PβNDTDTNT:PC₇₁BM‐based device with a moderate PCE of 3.6%.     

Tunable Crystallinity in Regioregular Poly(3‐Hexylthiophene) Thin Films and Its Impact on Field Effect Mobility

The properties of poly(alkylthiophenes) in solution are found to have a profound impact on the self assembly process and thus the microstructural and electrical properties of the resultant thin films. Ordered supramolecular precursors can be formed in regioregular poly(3‐hexylthiophene) (P3HT) solutions through the application of low intensity ultrasound. These precursors survive the casting process, resulting in a dramatic increase in the degree of crystallinity of the thin films obtained by spin coating. The crystallinity of the films is tunable, with a continuous evolution of mesoscale structures observed as a function of ultrasonic irradiation time. The photophysical properties of P3HT in solution as well in the solid state suggest that the application of ultrasound leads to a π stacking induced molecular aggregation resulting in field effect mobilities as high as 0.03 cm² V^?1 s^?1. A multiphase morphology, comprising short quasi‐ordered and larger, ordered nanofibrils embedded in a disordered amorphous phase is formed as a result of irradiation for at least 1 min. Two distinct regions of charge transport are identified, characterized by an initial sharp increase in the field effect mobility by two orders of magnitude due to an increase in crystallinity up to the percolation limit, followed by a gradual saturation where the mobility becomes independent of the thin film microstructure.     

Ultraviolet‐Light‐Induced Reversible and Stable Carrier Modulation in MoS2 Field‐Effect Transistors

The tuning of charge carrier concentrations in semiconductor is necessary in order to approach high performance of the electronic and optoelectronic devices. It is demonstrated that the charge‐carrier density of single‐layer (SL), bilayer (BL), and few‐layer (FL) MoS₂ nanosheets can be finely and reversibly tuned with N₂ and O₂ gas in the presence of deep‐ultraviolet (DUV) light. After exposure to N₂ gas in the presence of DUV light, the threshold voltages of SL, BL, and FL MoS₂ field‐effect transistors (FETs) shift towards negative gate voltages. The exposure to N₂ gas in the presence of DUV light notably improves the drain‐to‐source current, carrier density, and charge‐carrier mobility for SL, BL, and FL MoS₂ FETs. Subsequently, the same devices are exposed to O₂ gas in the presence of DUV light for different periods and the electrical characteristics are completely recovered after a certain time. The doping by using the combination of N₂ and O₂ gas with DUV light provides a stable, effective, and facile approach for improving the performance of MoS₂ electronic devices.     

A Multibeam Interference Model for Analyzing Complex Near‐Field Images of Polaritons in 2D van der Waals Microstructures

Van der Waals (vdW) materials are among the most promising candidates for photonic integrated circuits because they support a full set of polaritons that can manipulate light at deep subdiffraction nanoscale. It is possible to directly probe the propagating polaritons in vdW materials in real space via scattering‐type scanning near‐field optical microscopy, such that the wave vector and lifetime of the polaritons can be extracted from as‐measured interference fringes by Fourier analysis. However, this method is unsuitable for clutter interference patterns in samples exhibiting inadequate fringes due to small size (less than 10 µm) or complex edges that are often encountered in nanophotonic devices and new material characterization. Here, a multibeam interference model is developed to analyze complex images by disentangling them into periodic patterns and residue. By employing phase stationary approximation, polariton wave vector can be derived from offset ratio of the center point, and the ratio of polariton reflection and scattering rates at the edge is obtained from the ratio of the periodic and aperiodic patterns. This method can be widely used in the optical characterization of new vdW materials that are difficult to synthesize into large crystals, as well as nanophotonic integrated devices with unique boundaries.     

Self Encapsulated Poly(3‐hexylthiophene)‐poly(fluorinated alkyl methacrylate) Rod‐Coil Block Copolymers with High Field Effect Mobilities on Bare SiO2

Conjugated rod‐coil block copolymers provide an interesting route towards enhancing the properties of the conjugated block due to self‐assembly and the interplay of rod‐rod and rod‐coil interactions. Here, we demonstrate the ability of an attached semi‐fluorinated block to significantly improve upon the charge carrier properties of regioregular poly(3‐hexyl thiophene) (rr‐P3HT) materials on bare SiO₂. The thin film hole mobilities on bare SiO₂ dielectric surfaces of poly (3‐hexyl thiophene)‐block‐polyfluoromethacrylates (P3HT‐b‐PFMAs) can approach up to 0.12 cm² V^?1 s^?1 with only 33 wt% of the P3HT block incorporated in the copolymer, as compared to rr‐P3HT alone which typically has mobilities averaging 0.03 cm² V^?1 s^?1. To our knowledge, this is the highest mobility reported in literature for block copolymers containing a P3HT. More importantly, these high hole mobilities are achieved without multistep OTS treatments, argon protection, or post‐annealing conditions. Grazing incidence wide‐angle x‐ray scattering (GIWAX) data revealed that in the P3HT‐b‐PFMA copolymers, the P3HT rod block self‐assembles into highly ordered lamellar structures, similar to that of the rr‐P3HT homopolymer. Grazing incidence small‐angle x‐ray scattering (GISAXS) data revealed that lamellar structures are only observed in perpendicular direction with short PFMA blocks, while lamellae in both perpendicular and parallel directions are observed in polymers with longer PFMA blocks. AFM, GIWAXS, and contact angle measurements also indicate that PFMA block assembles at the polymer thin film surface and forms an encapsulation layer. The high charge carrier mobilities and the hydrophobic surface of the block copolymer films clearly demonstrates the influence of the coil block segment on device performance by balancing the crystallization and microphase separation in the bulk morphological structure.