Nematic Anisotropic Liquid‐Crystal Gels—Self‐Assembled Nanocomposites with High Electromechanical Response

The uniqueness of liquid crystals (LCs) lies in the large anisotropies of their properties, which can be utilized to generate high electromechanical responses. In a properly oriented LC polymer system, an external electric field can induce reorientation of the mesogenic units possessing a dielectric anisotropy, which, when coupled with the shape anisotropy of the mesogenic units, can in turn produce large mechanical strain. Anisotropic LC gels, which can be obtained by in‐situ photopolymerization of the reactive LC molecules in the presence of non‐reactive LC molecules in an oriented state, are an example of such liquid‐crystal polymer systems. It is shown here that a homeotropically aligned LC gel in its nematic phase exhibits high electrically induced strain (> 2 %) with an elastic modulus of 100 MPa and a high electromechanical conversion efficiency (75 %) under an electric field of 25 MV/m. These anisotropic LC polymeric materials could provide a technologically compatible system for such applications as artificial muscles and as microelectromechanical devices.     

Enhanced Dielectric and Electromechanical Responses in High Dielectric Constant All‐Polymer Percolative Composites

A type of all‐polymer percolative composite is introduced which exhibits a very high dielectric constant (> 7000). The experimental results also show that the dielectric behavior of this new class of percolative composites follows the predictions of the percolation theory and the analysis of conductive percolation phenomena. The very high dielectric constant of the all‐polymer composites, which are also very flexible and possesses an elastic modulus close to that of the insulation polymer matrix, makes it possible to induce a high electromechanical response under a very reduced electric field (a strain of 2.65 % with an elastic energy density of 0.18 J cm^–3 can be achieved under a field of 16 MV m^–1). Data analysis also suggests that within the composites, the non‐uniform local field distribution as well as interface effects can significantly enhance the strain responses. Furthermore, the experimental data as well as the data analysis indicate that conduction loss in the composites will not affect the strain hysteresis.     

Prestrain‐Free Dielectric Elastomers Based on Acrylic Thermoplastic Elastomer Gels: A Morphological and (Electro)Mechanical Property Study

Recent efforts have established that thermoplastic elastomer gels (TPEGs) composed of styrenic triblock copolymers swollen with a midblock‐selective solvent exhibit remarkable electromechanical properties as high‐performance dielectric elastomers. This class of electroactive polymers typically requires high electric fields for actuation, and a shortcoming that continues to thwart the widespread commercialization of such materials in general is the need to apply mechanical prestrain prior to electroactuation to decrease film thickness and, thus, the electric potential required to promote actuation. To alleviate this requirement, TPEGs consisting of acrylic triblock copolymers differing in molecular weight and composition, and swollen with a high dielectric, midblock‐selective solvent are investigated. Synchrotron small‐angle x‐ray scattering is used to probe the nanoscale morphologies of the resultant materials, and analysis of quasi‐static and cyclic tensile properties provides additional insight into both blend morphologies and electroactuation efficacy. Actuation strains measured in the absence of mechanical prestrain exceed 100% on an area basis, and electric fields capable of inducing actuation are as low as ～20 kV/mm. Failure occurs by either electromechanical instability or dielectric breakdown, depending on the copolymer and TPEG composition employed. The electromechanical properties of these acrylic‐based TPEGs match or exceed those of skeletal muscle, in which case they constitute an attractive and unexplored alternative to existing dielectric elastomers.     

Silicone–Poly(hexylthiophene) Blends as Elastomers with Enhanced Electromechanical Transduction Properties

Dielectric elastomers are progressively emerging as one of the best‐performing classes of electroactive polymers for electromechanical transduction. They are used for actuation devices driven by the so‐called Maxwell stress effect. At present, the need for high‐driving electric fields limits the use of these transduction materials in some areas of potential application, especially in the case of biomedical disciplines. A reduction of the driving fields may be achieved with new elastomers offering intrinsically superior electromechanical properties. So far, most attempts in this direction have been focused on the development of composites between elastomer matrixes and high‐permittivity ceramic fillers, yielding limited results. In this work, a different approach was adopted for increasing the electromechanical response of a common type of dielectric elastomer. The technique consisted in blending, rather than loading, the elastomer (poly(dimethylsiloxane)) with a highly polarizable conjugated polymer (undoped poly(3‐hexylthiophene)). The resulting material was characterised by dielectric spectroscopy, scanning electron microscopy, tensile mechanical analysis, and electromechanical transduction tests. Very low percentages (1–6 wt %) of poly(3‐hexylthiophene) yielded both an increase of the relative dielectric permittivity and an unexpected reduction of the tensile elastic modulus. Both these factors synergetically contributed to a remarkable increase of the electromechanical response, which reached a maximum at 1 wt % content of conjugated polymer. Estimations based on a simple linear model were compared with the experimental electromechanical data and a good agreement was found up to 1 wt %. This approach may lead to the development of new types of materials suitable for several types of applications requiring elastomers with improved electromechanical properties.     

Synergistic Improvement of Actuation Properties with Compatibilized High Permittivity Filler

Electroactive polymers can be used for actuators with many desirable features, including high electromechanical energy density, low weight, compactness, direct voltage control, and complete silence during actuation. These features may enable personalized robotics with much higher ability to delicately manipulate their surroundings than can be achieved with currently available actuators; however, much work is still necessary to enhance the electroactive materials. Electric field‐driven actuator materials are improved by an increase in permittivity and by a reduction in stiffness. Here, a synergistic enhancement method based on a macromolecular plasticizing filler molecule with a combination of both high dipole moment and compatibilizer moieties, synthesized to simultaneously ensure improvement of electromechanical properties and compatibility with the host matrix is presented. Measurements show an 85% increase in permittivity combined with 290% reduction in mechanical stiffness. NMR measurements confirm the structure of the filler while DSC measurements confirm that it is compatible with the host matrix at all the mixture ratios investigated. Actuation strain measurements in the pure shear configuration display an increase in sensitivity to the electrical field of more than 450%, confirming that the filler molecule does not only improve dielectric and mechanical properties, it also leads to a synergistic enhancement of actuation properties by simple means.     

Relaxor/Ferroelectric Composites: A Solution in the Quest for Practically Viable Lead‐Free Incipient Piezoceramics

Recently developed lead‐free incipient piezoceramics are promising candidates for off‐resonance actuator applications with their exceptionally large electromechanical strains. Their commercialization currently faces two major challenges: high electric field required for activating the large strains and large strain hysteresis. It is demonstrated that design of a relaxor/ferroelectric composite provides a highly effective way to resolve both challenges. Experimental results in conjunction with numerical simulations provide key parameters for the development of viable incipient piezoceramics.     

Temperature‐Insensitive (K,Na)NbO3‐Based Lead‐Free Piezoactuator Ceramics

The development of lead‐free piezoceramics has attracted great interest because of growing environmental concerns. A polymorphic phase transition (PPT) has been utilized in the past to tailor piezoelectric properties in lead‐free (K,Na)NbO₃ (KNN)‐based materials accepting the drawback of large temperature sensitivity. Here a material concept is reported, which yields an average piezoelectric coefficientd₃₃ of about 300 pC/N and a high level of unipolar strain up to 0.16% at room temperature. Most intriguingly, field‐induced strain varies less than 10% from room temperature to 175 °C. The temperature insensitivity of field‐induced strain is rationalized using an electrostrictive coupling to polarization amplitude while the temperature‐dependent piezoelectric coefficient is discussed using localized piezoresponse probed by piezoforce microscopy. This discovery opens a new development window for temperature‐insensitive piezoelectric actuators despite the presence of a polymorphic phase transition around room temperature.     

New Silicone Composites for Dielectric Elastomer Actuator Applications In Competition with Acrylic Foil

Several polydimethylsiloxane elastomers were developed and investigated regarding their potential use as materials in dielectric elastomer actuators (DEA). A hydroxyl end‐functionalized polydimethylsiloxane was reacted with different crosslinkers and the electromechanical properties of the resulting elastomers were investigated. The silicone showing the best actuation at the lowest electric field was further used as matrix and compounded with encapsulated conductive polyaniline particles. These composites have enhanced properties including increased strain at break, higher dielectric constant as well as, gratifyingly, breakdown fields higher than that of the matrix. One of the newly synthesized composites is compared to the commercially available acrylic foil VHB 4905 (3M) which is currently the most commonly used elastomer for DEA applications. It was found that this material has little hysteresis and can be activated at lower voltages compared to VHB 4905. For example, when the newly synthesized composite was 30% prestrained, a lateral actuation strain of about 12% at 40 V μm^?1 was measured while half of this actuation strain at the same voltage was measured for VHB 4905 film that was 300% prestrained. It also survived more than 100 000 cycles at voltages which are close to the breakdown field. Such materials might find applications wherever small forces but large strains at low voltages are required, in, for example, tactile displays.     

Electromagnetic field photonic sensors

In this paper, we review the different configurations proposed for electromagnetic field optical sensing. Intrinsic and extrinsic optical fiber sensors for electric and magnetic field measurement are examined, including those realized jacketing the fiber by magnetostrictive, conductive, electrochromic and polymeric materials and those measuring induced strain by magnetostrictive, electrostrictive and piezoelectric transducers. Extrinsic optical fiber sensors exploiting magneto-optic, electro-optic and Joule effects are also presented.Moreover, integrated optical electric and magnetic field sensors in which microwave signal provided by an antenna modulates the optical signal generated by an optical source are reviewed. Finally, active and coupled resonators based on electric field sensors are investigated.     

Enhanced Sensitivity of Capacitive Pressure and Strain Sensor Based on CaCu3Ti4O12 Wrapped Hybrid Sponge for Wearable Applications

Pressure sensors with highly sensitive and flexible characteristics have extensive applications in wearable electronics, soft robotics, human–machine interface, and more. Herein, an effective strategy is explored to enhance the sensitivity of the capacitive pressure sensor by fabricating a dielectric hybrid sponge consisting of calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO), a giant dielectric permittivity material, in polyurethane (PU). An ultrasoft CCTO@PU hybrid sponge is fabricated via dip‐coating the PU sponge into surface‐modified CCTO nanoparticles using 3‐aminopropyl triethoxysilane. The overall results show that the –NH₂ functionalized CCTO attributes proper adhesion of CCTO with the –OCN group of the PU to enhance interfacial polarization leading to a high dielectric permittivity (167.05) and low loss tangent (0.71) beneficial for flexible pressure sensing applications. Moreover, the as‐prepared CCTO@PU hybrid sponge at 30 wt% CCTO concentration exhibits excellent electromechanical properties with an ultralow compression modulus of 27.83 kPa and a high sensitivity of 0.73 kPa^?1 in a low‐pressure regime (<1.6 kPa). Finally, pressure and strain sensing performance is demonstrated for the detection of human activities by mounting the sensor on various parts of the human body. The work reveals a new opportunity for the facile fabrication of high performance CCTO‐based capacitive sensors with multifunctional properties.     

Self‐Repairable,High Permittivity Dielectric Elastomers with Large Actuation Strains at Low Electric Fields

A one‐step process for the synthesis of elastomers with high permittivity, excellent mechanical properties and increased electromechanical sensitivity is presented. It starts from a high molecular weight polymethylvinylsiloxane, P1 , whose vinyl groups serve two functions: the introduction of polar nitrile moieties by reacting P1 with 3‐mercaptopropionitrile ( 1 ) and the introduction of cross‐links to fine tune mechanical properties by reacting P1 with 2,2′‐(ethylenedioxy)diethanethiol ( 2 ). This twofold chemical modification furnished a material, C2 , with a powerful combination of properties: permittivity of up to 10.1 at 10⁴ Hz, elastic modulus Y_10% = 154 kPa, and strain at break of 260%. Actuators made of C2 show lateral actuation strains of 20.5% at an electric field as low as 10.8 V μm^–1. Additionally, such actuators can self‐repair after a breakdown, which is essential for an improved device lifetime and an attractive reliability. The actuators can be operated repeatedly and reversibly at voltages below the first breakdown. Due to the low actuation voltage and the large actuation strain applications of this material in commercial products might become reality.     

A Hybrid Material Approach Toward Solution‐Processable Dielectrics Exhibiting Enhanced Breakdown Strength and High Energy Density

The ever‐increasing demand for compact electronics and electrical power systems cannot be met with conventional dielectric materials with limited energy densities. Numerous efforts have been made to improve the energy densities of dielectrics by incorporating ceramic additives into polymer matrix. In spite of increased permittivities, thus‐fabricated polymer nanocomposites typically suffer from significantly decreased breakdown strengths, which preclude a substantial gain in energy density. Herein, organic–inorganic hybrids as a new class of dielectric materials are described, which are prepared from the covalent incorporation of tantalum species into ferroelectric polymers via in situ sol‐gel condensation. The solution‐processed hybrid with the optimal composition exhibits a Weibull breakdown strength of 505 MV m^?1 and a discharged energy density of 18 J cm^?3, which are more than 40% and 180%, respectively, greater than the pristine ferroelectric polymer. The superior performance is mainly ascribed to the deep traps created in the hybrids at the molecular level, which results in reduced electric conduction and lower remnant polarization. Simultaneously, the formation of the cross‐linked networks enhances the mechanical strengths of the hybrid films and thus hinders the occurrence of the electromechanical breakdown. This work opens up new opportunities to solution‐processed organic materials with high energy densities for capacitive electrical energy storage.     

The electrostrictor—A new type of electromechanical semiconductor oscillator

An investigation is carried out of unexpected electrical oscillations generated across germanium crystals which are subjected to strong electric fields; the latter are obtained by the application of a current pulse through a small area metallic electrode. The oscillations are found to be of electromechanical nature; i.e., it is shown that the electrical oscillations are accompanied with mechanical oscillations of the same frequency and, furthermore, that the latter have a definite phase relation with the former. The frequency of oscillation is identified as the mechanical natural frequency of vibration of the crystal-electrode combination. The electromechanical coupling in germanium is found to be due to a large electrostrictive property of this crystal. The electro-mechanical regenerative path responsible for the generation of oscillation is postulated to be due to the elastroresistance effect in germanium. Finally an electromechanical equivalent circuit for this novel device, called henceforth the electrostrictor, is derived predicting most of its experimentally observed characteristics.     

High Breakdown Field Dielectric Elastomer Actuators Using Encapsulated Polyaniline as High Dielectric Constant Filler

A novel method allowing rapid production of reliable composites with increased dielectric constant and high dielectric strength for dielectric elastomer actuators (DEA) is reported. The promising approach using composites of conductive particles and insulating polymers generally suffers from low breakdown fields when applied to DEA devices. The present publication shows how to overcome this deficiency by using conductive polyaniline (PANI) particles encapsulated into an insulating polymer shell prior to dispersion. PANI particles are encapsulated using miniemulsion polymerization (MP) of divinylbenzene (DVB). The encapsulation process is scaled up to approximately 20 g particles per batch. The resulting particles are used as high dielectric constant (?′) fillers. Composites in a polydimethylsiloxane (PDMS) matrix are prepared and the resulting films characterized by dielectric spectroscopy and tensile tests, and evaluated in electromechanical actuators. The composite films show a more than threefold increase in ?′, breakdown field strengths above 50 V μm^?1, and increased strain at break. These novel materials allow tuning the actuation strain or stress output and have potential as materials for energy harvesting.     

Tunable Dielectric Function in Electric‐Responsive Glass with Tree‐Like Percolating Pathways of Chargeable Conductive Nanoparticles

The design of nanostructured materials with specific physical properties is generally pursued by tuning nanoparticle size, concentration, or surface passivation. An important step forward is to realize “active” systems where nanoparticles are vehicles for controlling, in situ, some specific, tuneable features of a responsive functional material. In this perspective, this work focuses on the rational design of a nanostructured glass with electrically tuneable dielectric function obtained by injection and accumulation of charge on embedded conductive nanocrystals. This enables electrically controlled switching of semiconducting nanophases to charged polarisable states to be achieved, which could lead to smart, field‐enhancement applications in nanophotonics and plasmonics. Here, it is shown that such response switching can be obtained if a percolating charge‐transport mechanism is activated through a disordered tree‐like network, as is demonstrated to be possible in SiO₂ films where suitable dispersions of SnO₂ nanocrystals, with conductive interfaces, are obtained as a result of a new synthesis strategy.     

The Contributions of Polar Nanoregions to the Dielectric and Piezoelectric Responses in Domain‐Engineered Relaxor‐PbTiO3 Crystals

The existence of polar nanoregions is the most important characteristic of relaxor‐based ferroelectric materials. Recently, the contributions of polar nanoregions to the shear piezoelectric property of relaxor‐PbTiO₃ (PT) crystals are confirmed in a single domain state, accounting for 50%–80% of room temperature values. For electromechanical applications, however, the outstanding longitudinal piezoelectricity in domain‐engineered relaxor‐PT crystals is of the most significance. In this paper, the contributions of polar nanoregions to the longitudinal properties in [001]‐poled Pb(Mg_1/3Nb_2/3)O₃‐0.30PbTiO₃ and [110]‐poled Pb(Zn_1/3Nb_2/3)O₃‐0.15PbTiO₃ (PZN‐0.15PT) domain‐engineered crystals are studied. Taking the [110]‐poled tetragonal PZN‐0.15PT crystal as an example, phase‐field simulations of the domain structures and the longitudinal dielectric/piezoelectric responses are performed. According to the experimental results and phase‐field simulations, the contributions of polar nanoregions (PNRs) to the longitudinal properties of relaxor‐PT crystals are successfully explained on the mesoscale, where the PNRs behave as “seeds” to facilitate macroscopic polarization rotation and enhance electric‐field‐induced strain. The results reveal the importance of local structures to the macroscopic properties, where a modest structural variation on the nanoscale greatly impacts the macroscopic properties.     

各向异性压电陶瓷材料

本工作制备了添有少量Pb(Zn_(1/3) Nb_(2/3))O_3,Bi(Zn_(1/2) Ti_(1/2))O_3和MnO_2的高电阻率,高密度的改性(PbCa)TiO_3压电陶瓷。这种陶瓷在150℃和施加40—50kV/cm电场条件下极化之后显示出大的各向异性压电特性。它具有高的厚度扩张模式机电藕合系数Kt,高的机械品质因素Qm低的介电常数,而平面耦合系数Kp值极小。于是,这种新的压电材料适于制作高频陶瓷滤波器超声换能器,金属探伤检测器,以及声表面波器件等。     

Wafer bonded four‐junction GaInP/GaAs//GaInAsP/GaInAs concentrator solar cells with 44.7% efficiency

Triple‐junction solar cells from III–V compound semiconductors have thus far delivered the highest solar‐electric conversion efficiencies. Increasing the number of junctions generally offers the potential to reach even higher efficiencies, but material quality and the choice of bandgap energies turn out to be even more importance than the number of junctions. Several four‐junction solar cell architectures with optimum bandgap combination are found for lattice‐mismatched III–V semiconductors as high bandgap materials predominantly possess smaller lattice constant than low bandgap materials. Direct wafer bonding offers a new opportunity to combine such mismatched materials through a permanent, electrically conductive and optically transparent interface. In this work, a GaAs‐based top tandem solar cell structure was bonded to an InP‐based bottom tandem cell with a difference in lattice constant of 3.7%. The result is a GaInP/GaAs//GaInAsP/GaInAs four‐junction solar cell with a new record efficiency of 44.7% at 297‐times concentration of the AM1.5d (ASTM G173‐03) spectrum. This work demonstrates a successful pathway for reaching highest conversion efficiencies with III–V multi‐junction solar cells having four and in the future even more junctions. Copyright © 2014 John Wiley & Sons, Ltd.     

High Electric Field Carrier Transport and Power Dissipation in Multilayer Black Phosphorus Field Effect Transistor with Dielectric Engineering

This study addresses high electric field transport in multilayer black phosphorus (BP) field effect transistors with self‐heating and thermal spreading by dielectric engineering. Interestingly, a multilayer BP device on a SiO₂ substrate exhibits a maximum current density of 3.3 × 10¹⁰ A m^?2 at an electric field of 5.58 MV m^?1, several times higher than multilayer MoS₂. The breakdown thermometry analysis reveals that self‐heating is impeded along the BP–dielectric interface, resulting in a thermal plateau inside the channel and eventual Joule breakdown. Using a size‐dependent electro‐thermal transport model, an interfacial thermal conductance of 1–10 MW m^?2 K^?1 is extracted for the BP–dielectric interfaces. By using hexagonal boron nitride (hBN) as a dielectric material for BP instead of thermally resistive SiO₂ (κ ≈ 1.4 W m^?1 K^?1), a threefold increase in breakdown power density and a relatively higher electric field endurance is obtained together with efficient and homogenous thermal spreading because hBN has superior structural and thermal compatibility with BP. The authors further confirm the results based on micro‐Raman spectroscopy and atomic force microscopy, and observe that BP devices on hBN exhibit centrally localized hotspots with a breakdown temperature of 600 K, while the BP devices on SiO₂ exhibit hotspots in the vicinity of the electrode at 520 K.     

Ordered 3D Thin‐Shell Nanolattice Materials with Near‐Unity Refractive Indices

The refractive indices of naturally occurring materials are limited, and there exists an index gap between indices of air and available solid materials. With many photonics and electronics applications, there has been considerable effort in creating artificial materials with optical and dielectric properties similar to air while simultaneously being mechanically stable to bear load. Here, a class of ordered nanolattice materials consisting of periodic thin‐shell structures with near‐unity refractive index and high stiffness is demonstrated. Using a combination of 3D nanolithography and atomic layer deposition, these ordered nanostructured materials have reduced optical scattering and improved mechanical stability compared to existing randomly porous materials. Using ZnO and Al₂O₃ as the building materials, refractive indices from 1.3 down to 1.025 are achieved. The experimental data can be accurately described by Maxwell Garnett effective media theory, which can provide a guide for index design. The demonstrated low‐index, low‐scattering, and high‐stiffness materials can serve as high‐quality optical films in multilayer photonic structures, waveguides, resonators, and ultra‐low‐k dielectrics.