Electrical‐Polarization‐Induced Ultrahigh Responsivity Photodetectors Based on Graphene and Graphene Quantum Dots

Hybrid quantum dot–graphene photodetectors have recently attracted substantial interest because of their remarkable performance and low power consumption. However, the performance of the device greatly depends on the interfacial states and photogenerated screening field. As a consequence, the sensitivity is limited and the response time is relatively slow. In order to circumvent these challenges, herein, a composite graphene and graphene quantum dot (GQD) photodetector on lead zirconate titanate (Pb(Zr_0.2Ti_0.8)O₃) (PZT) substrates has been designed to form an ultrasensitive photodetector over a wide range of illumination power. Under 325 nm UV light illumination, the device shows sensitivity as high as 4.06 × 10⁹ A W^?1, which is 120 times higher than reported sensitivity of the same class of devices. Plant derived GQD has a broad range of absorptivity and is an excellent candidate for harvesting photons generating electron–hole pairs. Intrinsic electric field from PZT substrate separates photogenerated electron–hole pairs as well as provides the built‐in electric field that causes the holes to transfer to the underlying graphene channel. The composite structure of graphene and GQD on PZT substrate therefore produces a simple, stable, and highly sensitive photodetector over a wide range of power with short response time, which shows a way to obtain high‐performance optoelectronic devices.     

Room‐Temperature AFM Electric‐Field‐Induced Topotactic Transformation between Perovskite and Brownmillerite SrFeOx with Sub‐Micrometer Spatial Resolution

Reversible structural transformations between perovskite (PV) ABO_3?δ and brownmillerite (BM) ABO_2.5 (A = Ca²⁺, Sr²⁺; B = Fe^4+/3, Co^4+/3+) oxides can be induced by topotactic oxygen exchange at moderate temperatures under reducing/oxidizing conditions. The combination of a large oxide‐ion conductivity and a small free energy difference between the 4+/3+ oxidation states of many 3d transition metal ions enables these topotactic transformations. Herein, it is demonstrated that the electric field produced by a voltage‐biased atomic force microscopy tip can induce such transformation between PV SrFeO_3?δ and BM SrFeO_2.5 at room temperature and with sub‐micrometer spatial resolution. Interestingly, the structural transformation is kept after the electric field is removed, allowing a nonvolatile control of the local chemical, electrical, optical, and magnetic properties. Thus, the results presented in this paper open the door for the fabrication of stable ionic‐based devices through the electric field patterning of different crystallographic phases.     

Catalyst‐Free Synthesis of Few‐Layer Graphdiyne Using a Microwave‐Induced Temperature Gradient at a Solid/Liquid Interface

Graphdiyne (GDY), a 2D carbon allotrope, is predicted to possess high carrier mobility and an intrinsic bandgap. However, the controlled synthesis of mono‐ or few‐layer GDY with good crystallinity remains challenging because of the instability of the monomers. Herein, a rapid and catalyst‐free synthetic method is presented for few‐layer GDY involving the use of a solid/liquid interface and a microwave‐induced temperature gradient. Sodium chloride, which can absorb microwave energy, is used as the solid substrate in a nonabsorbing solvent. A temperature gradient is formed at the solid/liquid interface under microwave irradiation, facilitating the cross‐coupling reaction of monomers at the solid surface and stabilizing the monomers in the bulk solution. Few‐layer GDY with an average thickness of less than 2 nm, a field‐effect mobility of 50.1 cm² V^?1 s^?1, and p‐type characteristics is successfully obtained. This wet chemical approach may be extended to the synthesis of other few‐layered 2D materials with improved quality.     

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.     

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.     

Nanoscale Insight Into Lead‐Free BNT‐BT‐xKNN

Piezoresponse force microscopy (PFM) is used to afford insight into the nanoscale electromechanical behavior of lead‐free piezoceramics. Materials based on Bi_1/2Na_1/2TiO₃ exhibit high strains mediated by a field‐induced phase transition. Using the band excitation technique the initial domain morphology, the poling behavior, the switching behavior, and the time‐dependent phase stability in the pseudo‐ternary system (1–x)(0.94Bi_1/2Na_1/2TiO₃‐0.06BaTiO₃)‐xK_0.5Na_0.5NbO₃ (0 <= x <= 18 mol%) are revealed. In the base material (x = 0 mol%), macroscopic domains and ferroelectric switching can be induced from the initial relaxor state with sufficiently high electric field, yielding large macroscopic remanent strain and polarization. The addition of KNN increases the threshold field required to induce long range order and decreases the stability thereof. For x = 3 mol% the field‐induced domains relax completely, which is also reflected in zero macroscopic remanence. Eventually, no long range order can be induced for x >= 3 mol%. This PFM study provides a novel perspective on the interplay between macroscopic and nanoscopic material properties in bulk lead‐free piezoceramics.     

Boosting Room‐Temperature Magneto‐Ionics in a Non‐Magnetic Oxide Semiconductor

Voltage control of magnetism through electric field‐induced oxygen motion (magneto‐ionics) could represent a significant breakthrough in the pursuit for new strategies to enhance energy efficiency in magnetically actuated devices. Boosting the induced changes in magnetization, magneto‐ionic rates and cyclability continue to be key challenges to turn magneto‐ionics into real applications. Here, it is demonstrated that room‐temperature magneto‐ionic effects in electrolyte‐gated paramagnetic Co₃O₄ films can be largely increased both in terms of generated magnetization (6 times larger) and speed (35 times faster) if the electric field is applied using an electrochemical capacitor configuration (utilizing an underlying conducting buffer layer) instead of placing the electric contacts at the side of the semiconductor (electric‐double‐layer transistor‐like configuration). This is due to the greater uniformity and strength of the electric field in the capacitor design. These results are appealing to widen the use of ion migration in technological applications such as neuromorphic computing or iontronics in general.     

Interesting Evidence for Template‐Induced Ferroelectric Behavior in Ultra‐Thin Titanium Dioxide Films Grown on (110) Neodymium Gallium Oxide Substrates

The first evidence for room‐temperature ferroelectric behavior in anatase‐phase titanium dioxide (a‐TiO₂) is reported. Behavior strongly indicative of ferroelectric characteristics is induced in ultra‐thin (20 nm to 80 nm) biaxially‐strained epitaxial films of a‐TiO₂ deposited by liquid injection chemical vapor deposition onto (110) neodymium gallium oxide (NGO) substrates. The films exhibit significant orthorhombic strain, as analyzed by X‐ray diffraction and high‐resolution transmission electron microscopy. The films on NGO show a switchable dielectric spontaneous polarization when probed by piezoresponse force microscopy (PFM), the ability to retain polarization information written into the film using the PFM tip for extended periods (several hours) and at elevated temperatures (up to 100 °C) without significant loss, and the disappearance of the polarization at a temperature between 180 and 200 °C, indicative of a Curie temperature within this range. This combination of effects constitutes strong experimental evidence for ferroelectric behavior, which has not hitherto been reported in a‐TiO₂ and opens up the possibility for a range of new applications. A model is presented for the effects of large in‐plane strains on the crystal structure of anatase which provides a possible explanation for the experimental observations.     

Hybrid Improper Ferroelectricity in Multiferroic Superlattices: Finite‐Temperature Properties and Electric‐Field‐Driven Switching of Polarization and Magnetization

The so‐called hybrid improper ferroelectricity (HIF) mechanism allows to create an electrical polarization by assembling two nonpolar materials within a superlattice. It may also lead to the control of the magnetization by an electric field when these two nonpolar materials are magnetic in nature, which is promising for the design of novel magneto‐electric devices. However, several issues of fundamental and technological importance are presently unknown in these hybrid improper ferroelectrics. Examples include the behaviors of its polarization and dielectric response with temperature, and the paths to switch both the polarization and magnetization under electric fields. Here, an effective Hamiltonian scheme is used to study the multiferroic properties of the model superlattice (BiFeO₃)₁/(NdFeO₃)₁. Along with the development of a novel Landau‐type potential, this approach allows to answer and understand all the aforementioned issues at both microscopic and macroscopic levels. In particular, the polarization and dielectric response are both found to adopt temperature dependences, close to the phase transition, that agree with the behavior expected for first‐order improper ferroelectrics. And most importantly, a five‐state path resulting in the switching of polarization and magnetization under an electric field, via the reversal of antiphase octahedral tiltings, is also identified.     

Distinctive Performance of Terahertz Photodetection Driven by Charge‐Density‐Wave Order in CVD‐Grown Tantalum Diselenide

The quantum behavior of carriers in solid is the foundation of modern electronic and optoelectronic technology, but it is still facing huge challenges within inherited single‐particle quantum processes working at the millimeter wave/terahertz (THz) band. Here, a straightforward strategy for the direct detection of millimeter wave/THz photons in a sub‐wavelength metal‐TaSe₂‐metal structure under strong interaction with a localized field of surface plasmon is proposed. By breaking the inversion symmetry under the perturbations of electric field and atomic reconstruction from van der Waals integration, the nonequilibrium electronic states under a radiant field can be manipulated in a collective fashion, leading to a large photocurrent responsivity over 40 A W^?1 and noise equivalent power less than 1 pW Hz^?1/2 even at room temperature. A more than 40‐fold enhancement in responsivity is achieved when transitioning from the normal phase to the CDW phase. The findings shed fresh light on the understanding of the delicate balance in the charge‐ordered phase, and facilitate the exploitation of a correlated electron system for optoelectronic applications in fields of security, remote sensing, and imaging.     

Magnetic Field‐Induced Phase Transformation in NiMnCoIn Magnetic Shape‐Memory Alloys—A New Actuation Mechanism with Large Work Output

Magnetic shape memory alloys (MSMAs) have recently been developed into a new class of functional materials that are capable of magnetic‐field‐induced actuation, mechanical sensing, magnetic refrigeration, and energy harvesting. In the present work, the magnetic &!hyphen;field‐induced martensitic phase transformation (FIPT) in Ni₄₅Mn_36.5Co₅In_13.5 MSMA single crystals is characterized as a new actuation mechanism with potential to result in ultra‐high actuation work outputs. The effects of the applied magnetic field on the transformation temperatures, magnetization, and superelastic response are investigated. The magnetic work output of NiMnCoIn alloys is determined to be more than 1 MJ m^?3 per Tesla, which is one order of magnitude higher than that of the most well‐known MSMAs, i.e., NiMnGa alloys. In addition, the work output of NiMnCoIn alloys is orientation independent, potentially surpassing the need for single crystals, and not limited by a saturation magnetic field, as opposed to NiMnGa MSMAs. Experimental and theoretical transformation strains and magnetostress levels are determined as a function of crystal orientation. It is found that [111]‐oriented crystals can demonstrate a magnetostress level of 140 MPa T^?1 with 1.2% axial strain under compression. These field‐induced stress and strain levels are significantly higher than those from existing piezoelectric and magnetostrictive actuators. A thermodynamical framework is introduced to comprehend the magnetic energy contributions during FIPT. The present work reveals that the magnetic FIPT mechanism is promising for magnetic actuation applications and provides new opportunities for applications requiring high actuation work‐outputs with relatively large actuation frequencies. One potential issue is the requirement for relatively high critical magnetic fields and field intervals (1.5–3 T) for the onset of FIPT and for reversible FIPT, respectively.     

Thermo‐Phototronic Effect Enhanced InP/ZnO Nanorod Heterojunction Solar Cells for Self‐Powered Wearable Electronics

Enhancing interfacial charge transfer by the inner electric field is crucial for improving photovoltaic performance of heterojunction solar cells. Recent studies are focusing on how to utilize piezo‐phototronic effect (strain‐induced inner electric field) to modulate the interfacial charge transfer, whereas the preservation of solar cells from structure damage and performance decline under long‐term strain becomes increasingly challenging. Here, without use of strain, a thermo‐phototronic effect is presented to enhance the interfacial charge transfer in InP/ZnO nanorod heterojunction solar cells. Under a temperature gradient of 3.5 °C across the device, the output current and voltage of the solar cell under weak light illumination are enhanced by 27.3 and 76%, respectively. Moreover, the performance enhancement can be further regulated by applying different temperature gradients. This study serves as proof‐of‐principle for the thermo‐phototronic effect and pushes forward the maximum utilization of solar energy by a one‐circuit‐based photovoltaic‐thermoelectric system.     

Electric Field‐Induced Oxidation of Ferromagnetic/Ferroelectric Interfaces

Composite multiferroics are a new class of material where magneto‐electric coupling is achieved by creating an interface between a ferromagnetic and a ferroelectric compound. The challenge of understanding the chemical and magnetic properties of such interface is a key to achieve good magneto‐electric coupling. The unique possibilities offered by isotope sensitive techniques are used to selectively investigate the interface's chemistry and magnetism in Fe/BaTiO₃ and Fe/LiNbO₃ systems during the application of an electric field. With a large enough electric field, a strong oxidation of Fe is triggered, which creates a magnetically dead interface. This leads to an irreversible decrease of the magneto‐electric coupling properties. Material parameters are identified that determine under which electric field the interface may be modified. The results are confirmed on the two systems and are expected to be widespread in this new class of hybrid material.     

Fabrication of Large‐Scale Single‐Crystalline PrB6 Nanorods and Their Temperature‐Dependent Electron Field Emission

A simple catalysis‐free approach that utilises a gas–solid reaction for the synthesis of large‐scale single‐crystalline PrB₆ nanorods using Pr and BCl₃ as starting materials is demonstrated. The nanorods exhibit a low turn‐on electric field (2.80 V µ‐b;m^?1 at 10 µ‐b;A cm^?2), a low threshold electric field (6.99 V µ‐b;m^?1 at 1 mA cm^?2), and a high current density (1.2 mA cm^?2 at 7.35 V µ‐b;m^?1) at room temperature (RT). The turn‐on and threshold electric field are found to decrease clearly from 2.80 to 0.95 and 6.99 to 3.55 V µ‐b;m^?1, respectively, while the emission current density increases significantly from 1.2 to 13.8 mA cm^?2 (at 7.35 V µ‐b;m^?1) with an increase in the ambient temperature from RT to 623 K. The field enhancement factor, emission current density, and the dependence of the effective work function with temperature are investigated. The possible mechanism of the temperature‐dependent emission from PrB₆ nanorods is discussed.     

Ti‐Doping to Reduce Conductivity in Bi0.85Nd0.15FeO3 Ceramics

In 2009, Karimi et al. reported that Bi_1‐xNd_xFeO₃ 0.15 ≤ x ≤ 0.25 exhibited a PbZrO₃ (PZ)‐like structure. These authors presented some preliminary electrical data for the PZ‐like composition but noted that the conductivity was too high to obtain radio‐frequency measurements representative of the intrinsic properties. In this study, Bi_0.85Nd_0.15Fe_1‐yTi_yO₃ (0 ≤ y ≤ 0.1) were investigated, in which Ti acted as a donor dopant on the B‐site. In contrast to the original study of Karimi et al., X‐ray diffraction (XRD) of Bi_0.85Nd_0.15FeO₃ revealed peaks which were attributed to a mixture of PZ‐like and rhombohedral structures. However, as the Ti (0 < y ≤ 0.05) concentration increased, the rhombohedral peaks disappeared and all intensities were attributed to the PZ‐like phase. For y = 0.1, broad XRD peaks indicated a significant decrease in effective diffracting volume. Electron diffraction confirmed that the PZ‐like phase was dominant for y ≤ 0.05, but for y = 0.1, an incommensurate structure was present, consistent with the broadened XRD peaks. The substitution of Fe³⁺ by Ti⁴⁺ decreased the dielectric loss at room temperature from >0.3 to <0.04 for all doped compositions, with a minimum (0.015) observed for y = 0.03. The decrease in dielectric loss was accompanied by a decrease in the room temperature bulk conductivity from ～1 mS cm^?1 to <1 μS cm^?1 and an increase in bulk activation energy from 0.29 to >1 eV. Plots of permittivity (?_r) versus temperature for 0.01 ≤ y ≤ 0.05 revealed a step rather than a peak in ?_r on heating at the same temperature determined for the antiferroelectric–paraelectric phase transition by differential scanning calorimetry. Finally, large electric fields were applied to all doped samples which resulted in a linear dependence of polarisation on the electric field similar to that obtained for PbZrO₃ ceramics under equivalent experimental conditions.     

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.     

Ultrahigh Energy‐Storage Density in Antiferroelectric Ceramics with Field‐Induced Multiphase Transitions

The excellent energy‐storage performance of ceramic capacitors, such as high‐power density, fast discharge speed, and the ability to operate over a broad temperature range, gives rise to their wide applications in different energy‐storage devices. In this work, the (Pb_0.98La_0.02)(Zr_0.55Sn_0.45)_0.995O₃ (PLZS) antiferroelectric (AFE) ceramics are prepared via a unique rolling machine approach. The field‐induced multiphase transitions are observed in polarization–electric field (P–E) hysteresis loops. All the PLZS AFE ceramics possess high energy‐storage densities and discharge efficiency (above 80%) with different sintering temperatures. Of particular significance is that an ultrahigh recoverable energy‐storage density of 10.4 J cm^‐3 and a high discharge efficiency of 87% are achieved at 40 kV mm^‐1 for PLZS ceramic with a thickness of 0.11 mm, sintered at 1175 °C, which are by far the highest values ever reported in bulk ceramics. Moreover, the corresponding ceramics exhibit a superior discharge current density of 1640 A cm^‐2 and ultrafast discharge speed (75 ns discharge period). This great improvement in energy‐storage performance is expected to expand the practical applications of dielectric ceramics in numerous electronic devices.     

Universal Polarization Switching Behavior of Disordered Ferroelectrics

Universal scaling features of polarization switching are established experimentally in rather different classes of disordered ferroelectrics: in well‐studied lead‐zirconate titanate (PZT) ferroelectrics, in recently synthesized Cu‐stabilized 0.94(Bi_1/2Na_1/2)TiO₃–0.06BaTiO₃ (BNT‐BT) relaxor ferroelectrics, and in classical organic ferroelectrics P(VDF‐TrFE). These scaling properties are explained by an extended concept of an inhomogeneous field mechanism (IFM) of polarization dynamics in ferroelectrics. Accordingly, disordered ferroelectrics exhibit a wide spectrum of characteristic switching times due to a statistical distribution of values of the local electric field. How this distribution can be extracted from polarization measurements is demonstrated. Generally, it is shown that the polarization response is primarily controlled by the statistical characteristics of disorder rather than by a temporal law of the local polarization switching.     

Metal‐Organic Framework Nanofilm for Mechanically Flexible Information Storage Applications

Metal‐organic frameworks (MOFs), which are formed by association of metal cations or clusters of cations (“nodes”) with soft organic bridging ligands (“linkers”), are a fascinating class of flexible crystalline hybrid materials offering potential strategy for the construction of flexible electronics. In this study, a high‐quality MOF nanofilm, HKUST‐1, on flexible gold‐coated polyethylene terephthalate substrates is fabricated using liquid phase epitaxy approach. Uniform and reproducible resistive switching effect, which can be sustained under the strain of as high as 2.8%, and over the wide temperature range of –70 to +70 °C, is observed for the first time in the all solid‐state Au/HKUST‐1/Au/thin film structures. Through conductive atomic force microscopic and depth‐profiling X‐ray photoelectron spectroscopicanalysis, it is proposed that the electric field‐induced migration of the Cu_­²⁺ ions, which may lead to subsequent pyrolysis of the trimesic acid linkers and thus the formation of highly conducting filaments, could be the possible origin for the observed uniform resistance switching in HKUST‐1 nanofilms.     

Gate‐Induced Massive and Reversible Phase Transition of VO2 Channels Using Solid‐State Proton Electrolytes

The use of gate bias to control electronic phases in VO₂, an archetypical correlated oxide, offers a powerful method to probe their underlying physics, as well as for the potential to develop novel electronic devices. Up to date, purely electrostatic gating in 3‐terminal devices with correlated channel shows the limited electrostatic gating efficiency due to insufficiently induced carrier density and short electrostatic screening length. Here massive and reversible conductance modulation is shown in a VO₂ channel by applying gate bias V_G at low voltage by a solid‐state proton (H⁺) conductor. By using porous silica to modulate H⁺ concentration in VO₂, gate‐induced reversible insulator‐to‐metal (I‐to‐M) phase transition at low voltage, and unprecedented two‐step insulator‐to‐metal‐to‐insulator (I‐to‐M‐to‐I) phase transition at high voltage are shown. V_G strongly and efficiently injects H⁺ into the VO₂ channel without creating oxygen deficiencies; this H⁺‐induced electronic phase transition occurs by giant modulation (≈7%) of out‐of‐plane lattice parameters as a result of H⁺‐induced chemical expansion. The results clarify the role of H⁺ on the electronic state of the correlated phases, and demonstrate the potentials for electronic devices that use ionic/electronic coupling.