一种改进型1-3-2压电复合材料的研究

高质量的压电换能器需要具备较高的机电耦合系数和灵敏度。该文在传统型1-3-2压电复合材料的基础上提出了一种改进型1-3-2压电材料,提高了压电换能器的机电耦合系数和换能器的接收灵敏度。通过有限元仿真分析了不同间距对改进型1-3-2压电材料敏感元件的谐振频率、反谐振频率及机电耦合系数的影响,并与传统1-3-2型压电复合材料进行了对比。结果表明,与传统型1-3-2压电复合材料相比,在相同间距条件下,改进型压电材料的机电耦合系数约大0.03。制做的3种不同间距改进型压电材料表明,间距为1 mm的改进型压电材料的机电耦合系数较大,约为0.68。     

Cross‐Linked Gold Nanoparticle Composite Membranes as Highly Sensitive Pressure Sensors

In this article, highly sensitive differential pressure sensors based on free‐standing membranes of cross‐linked gold nanoparticles are demonstrated. The nanoparticle membranes are employed as both diaphragms and resistive transducers. The elasticity and the pronounced resistive strain sensitivity of these nanometer‐thin composites enable the fabrication of sensors achieving high sensitivities exceeding 10^?3 mbar^?1 while maintaining an overall small membrane area. Furthermore, by combining micro‐bulge tests with atomic force microscopy and in situ resistance measurements the membranes’ electromechanical responses are studied through precise observation of the concomitant changes of the membranes’ topography. The study demonstrates the high potential of free‐standing nanoparticle composites for the fabrication of highly sensitive force and pressure sensors and introduces a unique and powerful method for the electromechanical investigation of these materials.     

Theoretical Model and Outstanding Performance from Constructive Piezoelectric and Triboelectric Mechanism in Electrospun PVDF Fiber Film

Flexible materials with high electromechanical coupling performance are highly demanded for wide applications for electromechanical sensors and transducers, including mechanical energy harvesters. Here, outstanding electromechanical performance is obtained in electrospun‐aligned polyvinylidene fluoride (PVDF) fiber film. A theoretical model is developed from systematic theoretical analyses to clarify the underlying constructive piezoelectric‐triboelectric mechanism in the polarized PVDF fiber films that explains the experimental observations well. The electrospinning process induces polarization alignment and thus tunes the electron affinity for PVDF fibers with different polarization terminals, which results in the constructive piezoelectric and triboelectric responses in the obtained PVDF fiber films. Extremely large effective piezoelectric performance properties are achieved in the direct piezoelectric measurements, reaching the maximum effective piezoelectric strain and voltage coefficients of ?1065 pm V^?1 and ?9178 V mm N^?1, respectively, at 100 Hz. In the converse piezoelectric measurements without a significant contribution from reversible triboelectric effect, the maximum effective piezoelectric strain and voltage coefficients are ?166 pm V^?1 and ?1499 V mm N^?1, respectively. The theoretical analyses and experimental results show the great potential of the electrospun aligned polar PVDF fiber material for various electromechanical device applications, particularly for mechanical energy harvesting.     

A Printable Metallic Current Collector for All‐Printed High‐Voltage Micro‐Supercapacitors: Instantaneous Surface Passivation by Flash‐Light‐Sintering Reaction

Recently, a printable power source that can be implemented on demand in integrated circuitries has gained tremendous attention to facilitate next‐generation, form‐factor free, miniaturized electronic systems. Among various energy storage units, a solid‐state micro‐supercapacitor with in‐plane device architecture has been recognized as a viable candidate with characteristic advantages of long cycle life‐time, high frequency response, and fast charge/discharge rate. However, to date, high performance, all‐printed micro‐supercapacitors have rarely been reported owing to an absence of printable current collector materials that can sustain high voltage conditions. In this study, a multidimensional printable particle mixture comprising Ni nanoparticles, Ni flakes, and a photoreactive polymer, polyvinylpyrrolidone is proposed. The highly conductive, printed metallic current collector is generated with a conductive surface passivation layer in a timescale of 10^?3 s by flash‐light sintering process. It is revealed that the resulting metallic current collector is stable at a voltage as high as 3 V in the carbon electrode‐based device, enabling the fabrication of an all‐printed solid‐state micro‐supercapacitor with an areal energy density of 79–23 mJ cm^?2 at an areal power density of 0.4–12.8 mW cm^?2. Arbitrarily designed device circuits can be generated on demand simply by using a digitally programmable printing process, without incorporation of additional interconnection lines.     

3D‐Printable Antimicrobial Composite Resins

3D printing is seen as a game‐changing manufacturing process in many domains, including general medicine and dentistry, but the integration of more complex functions into 3D‐printed materials remains lacking. Here, it is expanded on the repertoire of 3D‐printable materials to include antimicrobial polymer resins, which are essential for development of medical devices due to the high incidence of biomaterial‐associated infections. Monomers containing antimicrobial, positively charged quaternary ammonium groups with an appended alkyl chain are either directly copolymerized with conventional diurethanedimethacrylate/glycerol dimethacrylate (UDMA/GDMA) resin components by photocuring or prepolymerized as a linear chain for incorporation into a semi‐interpenetrating polymer network by light‐induced polymerization. For both strategies, dental 3D‐printed objects fabricated by a stereolithography process kill bacteria on contact when positively charged quaternary ammonium groups are incorporated into the photocurable UDMA/GDMA resins. Leaching of quaternary ammonium monomers copolymerized with UDMA/GDMA resins is limited and without biological consequences within 4–6 d, while biological consequences could be confined to 1 d when prepolymerized quaternary ammonium group containing chains are incorporated in a semi‐interpenetrating polymer network. Routine clinical handling and mechanical properties of the pristine polymer matrix are maintained upon incorporation of quaternary ammonium groups, qualifying the antimicrobially functionalized, 3D‐printable composite resins for clinical use.     

3D Bicontinuous Nanoporous Reduced Graphene Oxide for Highly Sensitive Photodetectors

Reduced graphene oxide (RGO) is an important graphene derivative for applications in photonics and optoelectronics because of the band gap created by chemical oxidation. However, most RGO materials made by chemically exfoliated graphite oxide are 2D flakes. Their optoelectronic performance deteriorates significantly as a result of weak light‐matter interaction and poor electrical contact between stacking flakes. Here we report a bicontinuous 3D nanoporous RGO (3D np‐RGO) with high optoelectronic performance for highly sensitive photodetectors. 3D np‐RGO demonstrates a over 40 times higher light absorption than monolayer graphene materials and at least two orders of magnitude higher electron mobility than conventional RGO from discrete RGO flakes. The np‐RGO with an optimal reduction state shows ultrahigh photoresponse of 3.10 3 10⁴ A W^?1 at room temperature, approximately four orders of magnitude higher than graphene and other graphene derivatives at similar levels of light intensity radiations, and the excellent external quantum efficiency of 1.04 3 10⁷% better than commercial silicon photodetector. The ultrahigh capability of conversing photons to photocurrent originates from strongly enhanced light absorption, facilitated photocarrier transport, and tunable oxygenous defects and reduction states in the 3D interconnected bicontinuous RGO network.     

Light‐Emitting Devices Based on Electrochemiluminescence Gels

Electrochemiluminescence (ECL) is a self‐emission of light from electrochemically excited luminophores via a series of redox reactions. Over the past decade, light‐emitting devices based on gel‐phase ECL active materials, i.e., gel electrolyte composites (referred to as ECL gels) containing an ECL luminophore, electrolyte, and network matrix, have attracted considerable attention as a complementary device platform to conventional electroluminescent devices for low‐cost printable displays and solid‐state light sources. Although the ECL phenomenon is extensively exploited in analytical diagnostics and sensing, the development of printable and fast‐response gel‐type luminescent materials may further expand the potential application of ECL in solid‐state flexible, bendable, and stretchable light‐emitting devices. This review summarizes the operation mechanisms of ECL‐based light‐emitting devices, ECL emitters and electrolytes, engineering strategies for obtaining printable high‐strength/high‐conductivity ECL gels, and emerging applications of gel‐type ECL devices.     

A Review of 3D Printing Technologies for Soft Polymer Materials

Soft polymer materials, which are similar to human tissues, have played critical roles in modern interdisciplinary research. Compared with conventional methods, 3D printing allows rapid prototyping and mass customization and is ideal for processing soft polymer materials. However, 3D printing of soft polymer materials is still in the early stages of development and is facing many challenges including limited printable materials, low printing resolution and speed, and poor functionalities. The present review aims to summarize the ideas to address these challenges. It focuses on three points: 1) how to develop printable materials and make unprintable materials printable, 2) how to choose suitable methods and improve printing resolution, and 3) how to directly construct functional structures/systems with 3D printing. After a brief introduction on this topic, the mainstream 3D printing technologies for printing soft polymer materials are reviewed, with an emphasis on improving printing resolution and speed, choosing suitable printing techniques, developing printable materials, and printing multiple materials. Moreover, the state‐of‐the‐art advancements in multimaterial 3D printing of soft polymer materials are summarized. Furthermore, the revolutions brought about by 3D printing of soft polymer materials for applications similar to biology are highlighted. Finally, viewpoints and future perspectives for this emerging field are discussed.     

Flexible Piezoelectric Nanocomposite Generators Based on Formamidinium Lead Halide Perovskite Nanoparticles

Organic–inorganic lead halide perovskite materials have recently attracted much attention in the field of optoelectronic devices. Here, a hybrid piezoelectric nanogenerator based on a composite of piezoelectric formamidinium lead halide perovskite (FAPbBr₃) nanoparticles and polydimethylsiloxane polymer is fabricated. Piezoresponse force spectroscopy measurements reveal that the FAPbBr₃ nanoparticles contain well‐developed ferroelectric properties with high piezoelectric charge coefficient (d₃₃) of 25 pmV⁻¹. The flexible device exhibits high performance with a maximum recordable piezoelectric output voltage of 8.5 V and current density of 3.8 μA cm⁻² under periodically vertical compression and release operations. The alternating energy generated from nanogenerators can be used to charge a capacitor and light up a red light‐emitting diode through a bridge rectifier. This result innovatively expands the feasibility of organic–inorganic lead halide perovskite materials for application in a wide variety of high‐performance energy harvesting devices.     

Mobile Domain Walls as a Bridge between Nanoscale Conductivity and Macroscopic Electromechanical Response

The interfaces in complex oxides present unique properties exploitable in nanoscale devices. Recent studies on ferroelectric BiFeO₃, BaTiO₃, and Pb(Zr,Ti)O₃ have revealed an unusually high electric conductivity of the domain walls (DWs), adding another degree of freedom for controlling the local properties of these materials. While most of the investigations are focused on thin films for nanoscale applications, many practical devices, including piezoelectric sensors, actuators, and transducers, rely on the macroscopic properties of bulk polycrystalline materials where the average effect of local properties should be small. It is shown that in polycrystalline BiFeO₃ the local domain‐wall conductivity interferes with the dynamics of the DWs within the grains, resulting in an unexpectedly large effect on the macroscopic piezoelectric response. The results thus bridge the local conductivity and the macroscopic piezoelectricity via domain‐wall dynamics, revealing that the domain‐wall conductivity must be considered when interpreting and controlling macroscopic electromechanical properties.     

High‐Efficiency Water‐Transport Channels using the Synergistic Effect of a Hydrophilic Polymer and Graphene Oxide Laminates

Graphene oxide (GO) laminates possess unprecedented fast water‐transport channels. However, how to fully utilize these unique channels in order to maximize the separation properties of GO laminates remains a challenge. Here, a bio‐inspired membrane that couples an ultrathin surface water‐capturing polymeric layer (<10 nm) and GO laminates is designed. The proposed synergistic effect of highly enhanced water sorption from the polymeric layer and molecular channels from the GO laminates realizes fast and selective water transport through the integrated membrane. The prepared membrane exhibits highly selective water permeation with an excellent water flux of over 10 000 g m^?2 h^?1, which exceeds the performance upper bound of state‐of‐the‐art membranes for butanol dehydration. This bio‐inspired strategy demonstrated here opens the door to explore fast and selective channels derived from 2D or 3D materials for highly efficient molecular separation.     

AlN压电薄膜换能器性能的仿真研究

在压电换能器的制作中,电极对其谐振和反谐振频率、机电耦合系数及品质因数等重要性能有着直接的影响。该文针对AlN压电薄膜复合结构,采用COMSOL Multiphysics有限元软件对电极-AlN-不锈钢结构的三维模型进行了压电-结构耦合分析。基于此模型,通过改变电极厚度、材料及压电层的介电和机械损耗等参数,来研究换能器的性能参数变化,研究结果对后续以不锈钢为基底的压电超声换能器的制作起到了一定的理论指导作用。     

Volume Organization of Polymer and Hybrid Solar Cells as Revealed by Electron Tomography

Polymer and hybrid solar cells have the potential to become the leading technology of the 21^st century in conversion of sun light to electrical energy because their ease processing from solution producing printable devices in a roll‐to‐roll fashion with high speed and low cost. The performance of such devices critically depends on the nanoscale organization of the photoactive layer, which is composed of at least two functional materials: the electron donor and the electron acceptor forming a so‐called bulk heterojunction; however, control of its volume morphology still is a challenge. In this context, advanced analytical tools are required that are able to provide information on the local volume morphology of the photoactive layer with nanometer resolution. In this report electron tomography is introduced as the technique able to explore the 3D morphology of polymer and hybrid solar cells and the first results achieved are critically discussed.     

Smart Nanostructured Materials based on Self‐Assembly of Block Copolymers

Nanoscale fabrication of smart materials relying on the molecular self‐assembly of block copolymers (BCPs) has been recognized as a valuable platform for various next‐generation functional structures. In this Progress Report, the recent advances in the BCP self‐assembly process, which has paved the way for viable applications of emerging nanotechnologies, are highlighted. Effective light‐induced self‐assembly based on photothermal annealing of high‐χ BCPs and conformal 3D surface nanopatterning exploiting chemically modified graphene flexible substrates are reviewed as the typical instances of advanced BCP‐based nanofabrication methodologies. Additionally, relevant potential application fields are suggested, namely, graphene nanoribbon field effect transistors, highly tunable refractive index metasurfaces for visible light, high‐sensitivity surface‐enhanced Raman spectroscopy, 2D transition metal dichalcogenide nanopatterning, sequential infiltration synthesis, and organic photovoltaics. Finally, the future research direction as well as innovative applications of these smart nanostructured materials is proposed.     

Lightweight,Superelastic Boron Nitride/Polydimethylsiloxane Foam as Air Dielectric Substitute for Multifunctional Capacitive Sensor Applications

Porous polymeric foams as dielectric layer for highly sensitive capacitive based pressure sensors have been extensively explored owing to their excellent flexibility and elasticity. Despite intensive efforts, most of previously reported porous polymer foams still suffer from difficulty in further lowering the attainable density limit of ≈0.1 g cm^?3 while retaining high sensitivity and compressibility due to the limitations on existing fabrication techniques and materials. Herein, utilizing 3D interconnected networks of few‐layer hexagonal boron nitride foams (h‐BNFs) as supporting frameworks, lightweight and highly porous BN/polydimethylsiloxane composite foams (BNF@PDMS) with densities reaching as low as 15 mg cm^?3 and permittivity close to that of air are fabricated. This is the lightest PDMS‐based foam reported to date. Owing to the synergistic effects between BN and PDMS, these lightweight composite foams possess excellent mechanical resilience, extremely high compressibility (up to 95% strain), good cyclic performance, and superelasticity. Being electrically nonconductive, the potential application of BNF@PDMS as a dielectric layer for capacitive sensors is further demonstrated. Remarkably, the as‐fabricated device can perform multiple sensing functions such as noncontact touch sensor, environmental monitoring sensor, and high sensitivity pressure sensor that can detect extremely low pressures of below 1 Pa.     

Densely Interconnected Porous BN Frameworks for Multifunctional and Isotropically Thermoconductive Polymer Composites

Ideal materials for modern electronics packaging should be highly thermoconductive. This may be achieved through designing multifunctional polymer composites. Such composites may generally be achieved via effective embedment of functional inorganic fillers into desirable polymeric bodies. Herein, two types of high‐performance 3D h‐BN porous frameworks (3D‐BN), namely, h‐BN nanorod‐assembled networks and nanosheet‐interconnected frameworks, are successfully created via an in situ carbothermal reduction chemical vapor deposition substitution reaction using carbon‐based nanorod‐interconnected networks as templates. These 3D‐BN porous materials with densely interlinked frameworks, excellent mechanical robustness and integrity, highly isotropous and multiple heat transfer paths, enable reliable fabrications of diverse 3D‐BN/polymer porous composites. The composites exhibit combinatorial multifunctional properties, such as excellent mechanical strength, light weight, ultralow coefficient of thermal expansion, highly isotropic thermal conductivities (≈26–51 multiples of pristine polymers), relatively low dielectric constants and super‐low dielectric losses, and high resistance to softening at elevated temperatures. In addition, the regarded 3D‐BN frameworks are easily recycled from their polymer composites, and may be reliably reutilized for multifunctional reuse. Thus, these materials should be valuable for new‐era advanced electronic packaging and related applications.     

Surface Plasmons and Visible Light Iniferter Initiated Polymerization for Nanolocal Functionalization of Mesoporous Separation Layers

Although the technological relevance of mesoporous ceramic polymer hybrid materials is well accepted, missing functionalization concepts enabling 3D nanoscale local control of polymer placement into mesoporous materials, including thin films, and ideally using controlled polymerization techniques limit the application potential. Here, nanolocal functionalization of mesoporous separation layers using controlled, visible light iniferter initiated polymerization allowing responsive polymer functionalization locally limited to the irradiated spot is introduced. Thereby, two visible light sensitive iniferters, s-p-trimethoxysilylbenzyl-S´-dodecyltrithiocarbonate and 4-cyano-4-((dodecylsulfanylthiocarbonyl)sulfanyl)pentanoic acid, are developed for polymer functionalization of mesoporous films in a grafting from and a grafting through approach. 3D nanolocal polymer placement close to the proximity of the plasmonic field source is demonstrated by combining these visible light iniferter initiated polymerizations with optical near field modes, such as localized surface plasmon resonance (LSPR). As the location of the LSPR in mesoporous films can be controlled by placing metal alloy nanoparticles into these films and film thicknesses can be adjusted, this strategy is applied for precise positioning of polymers into mesoporous films with nanolocal control in three dimensions and thus reduces the gap in precision of functional group positioning between technological and biological nanopores.     

Flexible Piezoelectric Touch Sensor by Alignment of Lead‐Free Alkaline Niobate Microcubes in PDMS

A highly sensitive, lead‐free, and flexible piezoelectric touch sensor is reported based on composite films of alkaline niobate K_0.485Na_0.485Li_0.03NbO₃ (KNLN) powders aligned in a polydimethylsiloxane (PDMS) matrix. KNLN powder is fabricated by solid‐state sintering and consists of microcubes. The particles are dispersed in uncured PDMS and oriented by application of an oscillating dielectrophoretic alignment field. The dielectric constant of the composite film is almost independent of the microstructure, while upon alignment the piezoelectric charge coefficient increases more than tenfold up to 17 pC N^?1. A quantitative analysis shows that the origin is a reduction of the interparticle distance to under 1.0 µm in the aligned bicontinuous KNLN chains. The temperature stable piezoelectric voltage coefficient exhibits a maximum value of 220 mV m N^?1, at a volume fraction of only 10%. This state‐of‐the‐art value outperforms bulk piezoelectric ceramics and composites with randomly dispersed particles, and is comparable to the values reported for the piezoelectric polymers polyvinylidenefluoride and its random copolymer with trifluoroethylene. Optimized composite films are incorporated in flexible piezoelectric touch sensors. The high sensitivity is analyzed and discussed. As the fabrication technology is straightforward and easy to implement, applications are foreseen in flexible electronics such as wireless sensor networks and biodiagnostics.     

Acoustic Gain in Solids due to Piezoelectricity,Flexoelectricity, and Electrostriction

A quantitative discussion of the combined influence of three electromechanical effects: piezoelectricity, flexoelectricity, and electrostriction in solids is provided for acoustic absorption and gain. While piezoelectricity occurs in non‐centrosymmetric materials only, flexoelectricity and electrostriction exist in all materials. Two important new results are demonstrated: 1) the possibility to realize acoustic gain in all materials (centrosymmetric and non‐centrosymmetric) when the acoustic Cherenkov condition is fulfilled, and 2) realization of acoustic gain in the presence of a strong dc electric field, even when the Cherenkov condition is not fulfilled, in the case of strong cross‐coupling between piezoelectricity, flexoelectricity, and electrostriction. A simple analytical expression for the acoustic dispersion relation is derived for the combined effect of piezoelectricity, flexoelectricity, and electrostriction. At lower frequencies, the piezoelectric effect dominates for inversion‐asymmetric materials. At high frequencies (≈>1 MHz) flexoelectricity becomes increasingly important and eventually provides a major mechanism for gain and absorption in barium titanate (BaTiO₃). In the presence of strong electric fields (≈>1 MV m^?1), electrostriction provides a dominant isolated contribution to absorption/gain in BaTiO₃. Strong coupling between the three electromechanical contributions determines the total absorption/gain coefficient.     

Position‐Sensitive Array Photodetector Based on Comb‐Like CdS Nanostructure with Cone‐Shape Branches

2D microscale position‐sensitive detectors (PSDs) are highly desirable with the degree of integration increase and the size reduction of nanodevices, which are still unavailable. Multichannel devices with outstanding photoelectric properties attract considerable interest as powerful building blocks to be applied in on‐chip systems. Here, based on a highly ordered comb‐like CdS nanowire array with cone‐shape branches through a one‐step synthesis strategy, a high‐resolution 2D position‐sensitive photodetector is realized through variable resistance in different transportation routes and variable optical responses at different parts of the cone‐shape branches, which enable accurate position identification of incident light in various zones of nanowire arrays according to photocurrent changes. In a broadband from 310 to 560 nm, the PSD exhibits high sensitivity with 85 and 58 KΩ µm^?1 in the trunk and branch part, respectively, and an ultrafast optical response shorter than tens of millisecond. Moreover, a lower conductivity change rate per unit temperature of the PSD (1.625 × 10^?9 A V^?1 K^?1) than that of commercial Si‐based PSDs (≈6.67 × 10^?7 A V^?1 K^?1) reveals outstanding low‐temperature performance. Finally, the multichannel nanostructure based PSD with nanoscale resolution is applied to high‐accuracy quadrant photodetectors.