Tunable Photonic Materials via Monitoring Step‐Growth Polymerization Kinetics by Structural Colors

The functional and responsive properties of elastomeric materials highly depend on crosslink density and molecular weight between crosslinks. However, tedious analytical steps are needed to obtain polymer network structure–property relationships. In this article, an in situ structure–property characterization method is reported by monitoring the structural color change in a photonic elastomeric material. The photonic materials are prepared in a two‐step polymerization process. First, linear chain extension occurs via Michael addition. Second, photopolymerization ensures crosslinking, resulting in the formation of an elastomeric photonic network. During the first step, the step‐growth polymer process can be monitored by following the photonic reflection band redshift, allowing to program the molecular weight between the crosslinks. During network formation, the crosslink density, chain length between crosslinks, and the colors are “frozen in.” These processes can be locally controlled creating both single‐layered multicolor patterned and broadband reflective coatings at room temperature. The scalability of the coating process is further demonstrated by using a gravure printing technique. Additionally, the final coatings are made responsive toward specific solvents and temperature. Here the modulus, response, and color of the coating are controlled by tuning the crosslink density and molecular weight between crosslinks of the elastomeric material.     

Tunable Hierarchical Metallic‐Glass Nanostructures

Synthesizing metallic nanostructures with control over morphology, surface chemistry, and length‐scale is important for a wide range of applications. Nanostructures having large surface area paired with suitable chemistry are particularly desirable in catalytic applications to facilitate the reaction kinetics. However, the techniques used for nanostructure synthesis are often lengthy, difficult, require expensive precursors/stabilizers, and limit the control over nanostructure morphology/chemistry. Here tuning metallic‐glass nanostructures to a wide range of morphologies, where the surface is enriched with catalytic noble metal, is reported. By combining thermoplastic nanofabrication together with electrochemical processing, hierarchical metallic nanostructures with large electrochemical surface area and high catalytic activity are synthesized. Due to the versatility in processing and independent control over multiple length‐scales, the approach may serve as a tool‐box for fabricating complex hierarchical nanostructures for wide ranging applications.     

A Versatile Approach towards Multifunctional Robust Microcapsules with Tunable,Restorable, and Solvent‐Proof Superhydrophobicity for Self‐Healing and Self‐Cleaning Coatings

Numerous microencapsulation techniques have been developed to encase various chemicals, for which specific processing parameters are required to address the widely differing features of the encapsulated materials. Microencapsulation of reactive agents is a powerful technique that has been extensively applied to self‐healing materials. However, the poor solvent compatibility and insufficient thermal stability of microcapsules continue to pose challenges for long‐term storage, processing, and service in practical applications. Here, an easily modifiable and highly versatile method is reported for preparing various chemicals filled poly(urea‐formaldehyde) microcapsules that exhibit superior tightness against solvents and heat and that possess widely tunable, repetitiously self‐restorable, and solvent‐proof superhydrophobicity. In addition, the low‐cost fabrication of biomimetic multifunctional smart coatings is demonstrated for self‐healing anticorrosion and self‐cleaning antifouling applications by directly dispersing the superhydrophobic microcapsules into and onto a polymer matrix. The methodology presented in this study should inspire the development of multifunctional intelligent materials for applications in related fields.     

Easily Processable and Programmable Responsive Semi‐Interpenetrating Liquid Crystalline Polymer Network Coatings with Changing Reflectivities and Surface Topographies

The fabrication of stimulus‐responsive coatings that change both reflectivity and topography is hampered by the lack of easy processable, patternable, and programmable elastomers. Here, an easily applied reflective coating based on a semi‐interpenetrating polymer network composed of a liquid crystal elastomer and a liquid crystal network (>15 wt%) is reported. The reflective wavelength of these polysiloxane elastomer photonic coatings can be readily programed by the concentration of chiral reactive mesogen dopant that forms the network. The coatings show a fast and reversible decrease in reflection band intensity with increasing temperature, which can be tuned by the polymer network density. In addition, hierarchical surface relief structures are prepared, which can be reversibly changed with temperature.     

Tunable Near‐Infrared Organic Nanowire Nanolasers

Organic semiconductor nanowires have inherent advantages, such as amenability to low‐cost, low‐temperature processing, and inherent four‐level energy systems, which will significantly contribute to the organic solid‐state lasers (OSSLs) and miniaturized laser devices. However, the realization of near‐infrared (NIR) organic nanowire lasers is always a big challenge due to the difficultly in fabrication of organic nanowires with diameters of ≈100 nm and material issues such as low photoluminescence quantum efficiency in the red‐NIR region. What is more, the achievement of wavelength‐tunable OSSLs has also encountered enormous challenge. This study first demonstrates the 720 nm NIR lasing with a low lasing threshold of ≈1.4 µJ cm^?2 from the organic single‐crystalline nanowires, which are self‐assembled from small organic molecules of (E )‐3‐(4‐(dimethylamino)‐2‐methoxyphenyl)‐1‐(1‐hydroxynaphthalen‐2‐yl)prop‐2‐en‐1‐one through a facile solution‐phase growth method. Notably, these individual nanowires' Fabry–Pérot cavity can alternatively provide the red‐NIR lasing action at 660 or 720 nm from the 0–1 or 0–2 radiative transition channels, and the single (660 or 720 nm)/dual‐wavelength (660 and 720 nm) laser action can be achieved by modulating the length of these organic nanowires due to the intrinsic self‐absorption. These easily‐fabricated organic nanowires are natural laser sources, which offer considerable promise for coherent light devices integrated on the optics microchip.     

Building‐Block Diversity in Polydopamine Underpins a Multifunctional Eumelanin‐Type Platform Tunable Through a Quinone Control Point

Rational approaches to engineering polydopamine films with tailored properties for surface coating and functionalization are currently challenged by the lack of detailed information about the polymer structure and the mechanism of buildup. Using an integrated chemical and spectroscopic approach enables the demonstration of: a) a three‐component structure of polydopamine, comprising uncyclized (catecholamine) and cyclized (indole) units, as well as novel pyrrolecarboxylic acid moieties; b) remarkable variations in the relative proportions of the cyclized and uncyclized units with starting dopamine concentration; c) the occurrence of oligomer components up to the tetramer level; d) the covalent incorporation of Tris buffer; and e) the role of dopamine quinone as a crucial control point for directing the buildup pathways and tuning the properties. The importance of the uncyclized amine‐containing units in polydopamine adhesion is also highlighted. The proper selection of substrate concentration and buffer is thus proposed as a practical means of tailoring polydopamine functionality via control of competing pathways downstream of dopamine quinone.     

一种新颖的宽带可调光纤光栅滤波器

分析了光纤光栅（FBG）调谐的基本原理,进而采用新颖的调谐结构,设计并实现了一种宽带可调谐的FBG滤波器。该滤波器仅用1支FBG制做而成,其波长调谐范围最高可达40nm。实验结果表明,该FBG滤波器的调谐波长与调谐步进位移量之间具有良好的二次曲线关系。     

基于长周期光纤光栅的可调谐光滤波器设计

分析了长周期光纤光栅(LPFGs)透射谱受外界环境折射率变化影响的特性及其原理,进而提出了一种新型的可调谐光滤波器的设计思路．并运用分段光栅的矩阵分析法对其进行了具体的计算。此种光滤波器具有滤波精度高、可实现滤波波长和深度单独、连续调谐及全光纤性等优点,滤波波长调谐范围可达15nm,衰耗深度调谐范围达9dB。     

Current‐Mode Electronically Tunable Universal Filter Using Only Plus‐Type Current Controlled Conveyors and Grounded Capacitors

In this paper we present a new current‐mode electronically tunable universal filter using only plus‐type current controlled conveyors (CCCII+s) and grounded capacitors. The proposed circuit can simultaneously realize lowpass, bandpass, and highpass filter functions—all at high impedance outputs. The realization of a notch response does not require additional active elements. The circuit enjoys an independent current control of parameters ω₀ and ω₀ / Q. No element matching conditions are imposed. Both its active and passive sensitivities are low.     

Solid‐State NMR Investigations of the Unusual Effects Resulting from the Nanoconfinement of Water within Amphiphilic Crosslinked Polymer Networks

Two types of solid‐state ¹⁹F NMR spectroscopy experiments are used to characterize phase‐separated hyperbranched fluoropolymer–poly(ethylene glycol) (HBFP–PEG) crosslinked networks. Mobile (soft) domains are detected in the HBFP phase by a rotor‐synchronized Hahn echo under magic‐angle spinning conditions, and rigid (hard) domains by a solid echo with no magic‐angle spinning. The mobility of chains is detected in the PEG phase by ¹H → ¹³C cross‐polarization transfers with ¹H spin‐lock filters with and without magic‐angle spinning. The interface between HBFP and PEG phases is detected by a third experiment, which utilized a ¹⁹F → ¹H–(spin diffusion)–¹H → ¹³C double transfer with ¹³C solid‐echo detection. The results of these experiments show that composition‐dependent PEG inclusions in the HBFP glass rigidify on hydration, consistent with an increase in macroscopic tensile strength.     

Beam‐Induced Fe Nanopillars as Tunable Domain‐Wall Pinning Sites

Focused‐electron‐beam‐induced deposition (FEBID) is employed to create freestanding magnetic nanostructures. By growing Fe nanopillars on top of a perpendicular magnetic domain wall (DW) conduit, pinning of the DWs is observed due to the stray fields emanating from the nanopillar. Furthermore, a different DW pinning behavior is observed between the up and down magnetic states of the pillar, allowing to deduce the switching fields of the pillar in a novel way. The implications of these results are two‐fold: not only can 3‐dimensional nano‐objects be used to control DW motion in applications, it is also proposed that DW motion is a unique tool to probe the magnetic properties of nano‐objects.     

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.     

Tunable Crystal Nanostructures of Pentacene Thin Films on Gate Dielectrics Possessing Surface‐Order Control

To enhance the electrical performance of pentacene‐based field‐effect transistors (FETs) by tuning the surface‐induced ordering of pentacene crystals, we controlled the physical interactions at the semiconductor/gate dielectric (SiO₂) interface by inserting a hydrophobic self‐assembled monolayer (SAM, CH₃‐terminal) of organoalkyl‐silanes with an alkyl chain length of C8, C12, C16, or C18, as a complementary interlayer. We found that, depending on the physical structure of the dielectric surfaces, which was found to depend on the alkyl chain length of the SAM (ordered for C18 and disordered for C8), the pentacene nano‐layers in contact with the SAM could adopt two competing crystalline phases—a “thin‐film phase” and “bulk phase” – which affected the π‐conjugated nanostructures in the ultrathin and subsequently thick films. The field‐effect mobilities of the FET devices varied by more than a factor of 3 depending on the alkyl chain length of the SAM, reaching values as high as 0.6 cm² V^?1 s^?1 for the disordered SAM‐treated SiO₂ gate‐dielectric. This remarkable change in device performance can be explained by the production of well π‐conjugated and large crystal grains in the pentacene nanolayers formed on a disordered SAM surface. The enhanced electrical properties observed for systems with disordered SAMs can be attributed to the surfaces of these SAMs having fewer nucleation sites and a higher lateral diffusion rate of the first seeding pentacene molecules on the dielectric surfaces, due to the disordered and more mobile surface state of the short alkyl SAM.     

Protein‐Enabled Layer‐by‐Layer Syntheses of Aligned,Porous‐Wall,High‐Aspect‐Ratio TiO2 Nanotube Arrays

An aqueous, protein‐enabled (biomimetic), layer‐by‐layer titania deposition process is developed, for the first time, to convert aligned‐nanochannel templates into high‐aspect‐ratio, aligned nanotube arrays with thin (34 nm) walls composed of co‐continuous networks of pores and titania nanocrystals (15 nm ave. size). Alumina templates with aligned open nanochannels are exposed in an alternating fashion to aqueous protamine‐bearing and titania precursor‐bearing (Ti(IV) bis‐ammonium‐lactato‐dihydroxide, TiBALDH) solutions. The ability of protamine to bind to alumina and titania, and to induce the formation of a Ti–O‐bearing coating upon exposure to the TiBALDH precursor, enables the layer‐by‐layer deposition of a conformal protamine/Ti–O‐bearing coating on the nanochannel surfaces within the porous alumina template. Subsequent protamine pyrolysis yields coatings composed of co‐continuous networks of pores and titania nanoparticles. Selective dissolution of the underlying alumina template through the porous coating then yields freestanding, aligned, porous‐wall titania nanotube arrays. The interconnected pores within the nanotube walls allow enhanced loading of functional molecules (such as a Ru‐based N719 dye), whereas the interconnected titania nanoparticles enable the high‐aspect‐ratio, aligned nanotube arrays to be used as electrodes (as demonstrated for dye‐sensitized solar cells with power conversion efficiencies of 5.2 ± 0.4%).     

A Simple,One‐Step Approach to Durable and Robust Superhydrophobic Textiles

Superhydrophobic textile fabrics are prepared by a simple, one‐step gas phase coating procedure by which a layer of polymethylsilsesquioxane nanofilaments is grown onto the individual textile fibers. A total of 11 textile fabrics made from natural and man made fibers are successfully coated and their superhydrophobic properties evaluated by the water shedding angle technique. A thorough investigation of the commercially relevant poly(ethylene terephthalate) fabric reveals an unparalleled long‐term water resistance and stability of the superhydrophobic effect. Because of the special surface geometry generated by the nanoscopic, fibrous coating on the microscopic, fibrous textiles, the coated fabric remains completely dry even after two months of full immersion in water and stays superhydrophobic even after continuous rubbing with a skin simulating friction partner under significant load. Furthermore, important textile parameters such as tensile strength, color, and haptics are unaffected by the silicone nanofilament coating. For the first time, an in‐depth characterization of the wetting properties, beyond simple contact angle measurements, as well as a thorough evaluation of the most important textile parameters is performed on a superhydrophobic fabric, which reveals a true potential for application.     

基于可调F-P滤波器的光纤光栅传感器阵列查询技术

利用可调 F- P滤波器对四个光纤光栅组成的传感器阵列进行波长扫描 ,借助示波器和探测器对滤波光束的时序分布进行观察 ,实现地址查询。比较波长漂移前后传感阵列的反射谱 ,可用于解调 ,实验结果与预期值基本一致。选用反射率相差悬殊的光栅作传感元 ,有利于增加测量范围     

Nanostructured Metallo‐Dielectric Quasi‐Crystals: Towards Photonic‐Plasmonic Resonance Engineering

The first evidence of out‐of‐plane resonances in hybrid metallo‐dielectric quasi‐crystal (QC) nanostructures composed of metal‐backed aperiodically patterned low‐contrast dielectric layers is reported. Via experimental measurements and full‐wave numerical simulations, these resonant phenomena are characterized with specific reference to the Ammann‐Beenker (quasi‐ periodic, octagonal) tiling lattice geometry and the underlying physics is investigated. In particular, it is shown that, by comparison with standard periodic structures, a moderately richer spectrum of resonant modes may be excited, due to the easier achievement of phase‐matching conditions endowed by its denser Bragg spectrum. Such modes are characterized by a distinctive plasmonic or photonic behavior, discriminated by their field distribution and dependence on the metal film thickness. Moreover, the response is accurately predicted via computationally affordable periodic‐approximant‐based numerical modeling. The enhanced capability of QCs to control number, spectral position, and mode distribution of hybrid resonances may be exploited in a variety of possible applications. To assess this aspect, label‐free biosensing is studied via characterization of the surface sensitivity of the proposed structures with respect to local refractive index changes. Moreover, it is also shown that the resonance‐engineering capabilities of QC nanostructures may be effectively exploited in order to enhance the absorption efficiency of thin‐film solar cells.     

Porous Polymer Films with Gradient‐Refractive‐Index Structure for Broadband and Omnidirectional Antireflection Coatings

Porous polymer films that can be employed for broadband and omnidirectional antireflection coatings are successfully shown. These films form a gradient‐refractive‐index structure and are achieved by spin‐coating the solution of a polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA)/PMMA blend onto an octadecyltrichlorosilane (OTS)‐modified glass substrate. Thus, a gradient distribution of PMMA domains in the vertical direction of the entire microphase‐separated film is obtained. After those PMMA domains are removed, a PS porous structure with an excellent gradient porosity ratio in the vertical direction of the film is formed. Glass substrates coated with such porous polymer film exhibit both broadband and omnidirectional antireflection properties because the refractive index increases gradually from the top to the bottom of the film. An excellent transmittance of >97% for both visible and near‐infrared (NIR) light is achieved in these gradient‐refractive‐index structures. When the incident angle is increased, the total transmittance for three different incident angles is improved dramatically. Meanwhile, the film possesses a color reproduction character in the visible light range.