Bias-dependent photoresponse of Td-WTe2grown by chemical vapor deposition.

The type-II Weyl semimetal Td-WTe2is one of the wonder materials for high-performance optoelectronic devices. We report the self-powered Td-WTe2photodetectors and their bias-dependent photoresponse in the visible region (405, 520, 638 nm) driven by the bulk photovoltaic effect. The device shows the responsivity of 15.8 mAW-1and detectivity of 5.2 × 109Jones at 520 nm. Besides, the response time of the WTe2photodetector shows the strong bias-voltage dependent property. This work offers a physical reference for understanding the photoresponse process of Td-WTe2photodetectors.

Probing Effective Out-of-Plane Piezoelectricity in van der Waals Layered Materials Induced by Flexoelectricity.

Many van der Waals layered 2D materials, such as h-BN, transition metal dichalcogenides (TMDs), and group-III monochalcogenides, have been predicted to possess piezoelectric and mechanically flexible natures, which greatly motivates potential applications in piezotronic devices and nanogenerators. However, only intrinsic in-plane piezoelectricity exists in these 2D materials and the piezoelectric effect is confined in odd-layers of TMDs. The present work is intent on combining the free-standing design and piezoresponse force microscopy techniques to obtain and directly quantify the effective out-of-plane electromechanical coupling induced by strain gradient on atomically thin MoS2 and InSe flakes. Conspicuous piezoresponse and the measured piezoelectric coefficient with respect to the number of layers or thickness are systematically illustrated for both MoS2 and InSe flakes. Note that the promising effective piezoelectric coefficient (deff 33 ) of about 21.9 pm V-1 is observed on few-layered InSe. The out-of-plane piezoresponse arises from the net dipole moment along the normal direction of the curvature membrane induced by strain gradient. This work not only provides a feasible and flexible method to acquire and quantify the out-of-plane electromechanical coupling on van der Waals layered materials, but also paves the way to understand and tune the flexoelectric effect of 2D systems.

Large-Scale Growth and Field-Effect Transistors Electrical Engineering of Atomic-Layer SnS2.

2D layers of metal dichalcogenides are of considerable interest for high-performance electronic devices for their unique electronic properties and atomically thin geometry. 2D SnS2 nanosheets with a bandgap of ≈2.6 eV have been attracting intensive attention as one potential candidate for modern electrocatalysis, electronic, and/or optoelectronic fields. However, the controllable growth of large-size and high-quality SnS2 atomic layers still remains a challenge. Herein, a salt-assisted chemical vapor deposition method is provided to synthesize atomic-layer SnS2 with a large crystal size up to 410 µm and good uniformity. Particularly, the as-fabricated SnS2 nanosheet-based field-effect transistors (FETs) show high mobility (2.58 cm2 V-1 s-1 ) and high on/off ratio (≈108 ), which is superior to other reported SnS2 -based FETs. Additionally, the effects of temperature on the electrical properties are systematically investigated. It is shown that the scattering mechanism transforms from charged impurities scattering to electron-phonon scattering with the temperature. Moreover, SnS2 can serve as an ideal material for energy storage and catalyst support. The high performance together with controllable growth of SnS2 endow it with great potential for future applications in electrocatalysis, electronics, and optoelectronics.

Three-dimensional porous Co3O4-CoO@GO composite combined with N-doped carbon for superior lithium storage.

Transition metal oxides (TMOs) as anode materials have potential for lithium-ion batteries (LIBs). However, the poor rate capacity and cycle stability restrict its application. Herein, we demonstrate a facile one-step hydrothermal method to construct a three-dimensional porous conductive network structure, which consists of thin-layered graphene, ultrafine Co3O4-CoO nanoparticles and nitrogen-doped carbon. This unique structure can effectively prevent particle agglomeration and cracking caused by volume expansion, provide fast passage for lithium ion/electron transport during cycling and improve the electrical conductivity of the electrode. Moreover, the electrochemical kinetic analysis proves that this is a process dominated by pseudocapacitive behavior. Consequently, the N-C@Co3O4-CoO@GO hybrid electrode delivers an ultrahigh capacity of 1 273.1 mA h g-1 at 0.1 A g-1 and superior rate performance (725.1 mA h g-1 at 5 A g-1). Additionally, it exhibits a high reversible cycling capacity of 787.4 mA h g-1 at 1 A g-1 over 600 cycles and even maintains excellent cycling stability for a ultra-long cycles at 5 A g-1. This work provides a feasible strategy for fabricating the N-C@Co3O4-CoO@GO composite as a promising high-performance TMOs anode for LIBs.

Pseudocapacitive Li-ion storage boosts high-capacity and long-life performance in multi-layer CoFe2O4/rGO/C composite.

Due to the intrinsic low electrical conductivity and large volume expansion of the CoFe2O4 based active materials, designing more novel structures is still one of the most important challenges for its lithium ion battery application. In this work, the CoFe2O4/reduced graphene oxide/carbon (CFO/rGO/C) composite with integrated multi-layer structure has been synthesized through a facial two-step hydrothermal method. Benefiting from the introduction of the graphene network and amorphous carbon coating layer, as well as the accompanying synergistic effect, this composite can exhibit fast and reversible lithium intercalation/deintercalation reactions. With the aid of a surface-induced capacitive process, the CFO/rGO/C composite delivers a superior specific capacity (945 mA h g-1 at 0.1 A g-1) and excellent long-term cyclic stability (421 mA h g-1 at 4 A g-1 with closely 100% Coulombic efficiency after 2000 cycles). Significantly, at a high current density of 1 A g-1, the reversible capacity exhibits a rapid increasing after 100 cycles and finally shows an ultra-high-capacity of 1430 mA h g-1 over 500 cycles. This method could be generalized to the preparation of other similar transition metal oxide-based materials for the development of high-performance energy storage systems.

Probing electromechanical behaviors by datacube piezoresponse force microscopy in ambient and aqueous environments.

For assisting the in-depth investigations of widespread electromechanical phenomena in functional materials, piezoresponse force microscopy (PFM) has gradually evolved to realize full information-flow acquisition and fit the conductive liquid working environments. Here, we designed data cube (DCUBE) based PFM to collect the electromechanical effect into a high-dimensional array of piezoresponse by adding ac bias with a wide range of frequencies to the probe. The electromechanical and mechanical spectra can be consecutively extracted at each pixel in the intermittent-contact mode. High-resolution ferroelectric domains of the poled LiNbO3 were mapped, corresponding to the ideal phase contrasts of about 180° in air, decane, and deionized water. Rich information detection and non-contact mode in DCUBE-PFM bring many merits on the electromechanical characterizations, especially for elastic-inhomogeneous surfaces and soft materials. Moreover, we systematically reveal the Debye screening effect and time-resolved field-oriented ion dynamics, which play crucial roles in the reduction of PFM spatial resolution in electrolytes. These physical discussions provide strategies to further realize high-resolution electromechanical imaging in highly conductive liquid environments.

In situ exploration of the thermodynamic evolution properties in the type II interface from the WSe2-WS2 lateral heterojunction.

The mutual interaction of the type II heterointerface can be very susceptible to the variation of electron states, introducing differences into the band structure and the band alignment in comparison to their pristine states. Here, the thermal evolution of the exciton transition and electronic properties inside the covalently bonded type II interface of the atomically planar WSe2-WS2 lateral heterojunction has been studied. With the aid of luminescence and electronic evolution, it was found that the coupling at the heterointerface is strong, and that the change in the photon-electron transition with temperature is weak. Meanwhile, by employing some quantitative computational methods, the temperature variation of the extracted built-in electric field at the interface is unexpectedly pronounced, resulting from the thermodynamical spanning behaviors of the electrons, as well as the strains generated by the difference in the thermal expansion coefficient between the structural lattice. In addition, the electric contact at the interface shows a negative temperature correlation. The present findings provide a vital contribution to the photo-electron interaction-based application and evaluation paths of the electric contact in two-dimensional transition metal dichalcogenide-based devices.

Correction: Silver/silver halide supported on mesoporous ceria particles and photo-CWPO degradation under visible light for organic compounds in acrylonitrile wastewater.

[This corrects the article DOI: 10.1039/D1RA04465F.].

Phase transition in WSe2-xTex monolayers driven by charge injection and pressure: a first-principles study.

Alloying strategies permit new probes for governing structural stability and semiconductor-semimetal phase transition of transition metal dichalcogenides (TMDs). However, the possible structure and phase transition mechanism of the alloy TMDs, and the effect of an external field, have been still unclear. Here, the enrichment of the Te content in WSe2-xTex monolayers allows for coherent structural transition from the H phase to the T' phase. The crystal orbital Hamiltonian population (COHP) uncovers that the bonding state of the H phase approaches the high-energy domain near the Fermi level as the Te concentration increases, posing a source of structural instability followed by a weakened energy barrier for the phase transition. In addition, the structural phase transition driven by charge injection opens up new possibilities for the development of phase-change devices based on atomic thin films. For WSe2-xTex monolayers with the H phase as the stable phase, the critical value of electron concentration triggering the phase transition decreases with an increase in the x value. Furthermore, the energy barrier from the H phase to the T' phase can be effectively reduced by applying tensile strain, which could favor the phase switching in electronic devices. This work provides a critical reference for controllable modulation of phase-sensitive devices from alloy materials with rich phase characteristics.

Tunable Negative and Positive Photoconductance in Van Der Waals Heterostructure for Image Preprocessing.

The processing of visual information occurs mainly in the retina, and the retinal preprocessing function greatly improves the transmission quality and efficiency of visual information. The artificial retina system provides a promising path to efficient image processing. Here, graphene/InSe/h-BN heterogeneous structure is proposed, which exhibits negative and positive photoconductance (NPC and PPC) effects by altering the strength of a single wavelength laser. Moreover, a modified theoretical model is presented based on the power-dependent photoconductivity effect of laser: I ph = - mP α 1 + nP α 2 ${\rm I}_{\rm ph}\,=\,-{\rm mP}^{\alpha _{1}} + {\rm nP}^{\alpha _{2}}$ , which can reveal the internal physical mechanism of negative/positive photoconductance effects. The present 2D structure design allows the field effect transistor (FET) to exhibit excellent photoelectric performance (RNPC = 1.1× 104 AW-1, RPPC = 13 AW-1) and performance stability. Especially, the retinal pretreatment process is successfully simulated based on the negative and positive photoconductive effects. Moreover, the pulse signal input improves the device responsivity by 167%, and the transmission quality and efficiency of the visual signal can also be enhanced. This work provides a new design idea and direction for the construction of artificial vision, and lay a foundation for the integration of the next generation of optoelectronic devices.

Directly measuring flexoelectric coefficients µ11 of the van der Waals materials.

Flexoelectricity originates from the electromechanical coupling interaction between strain gradient and polarization, broadly applied in developing electromechanical and energy devices. However, the study of quantifying the longitudinal flexoelectric coefficient (µ11) which is important for the application of atomic-scale two-dimensional (2D) materials is still in a slow-moving stage, owing to the technical challenges. Based on the free-standing suspension structure, this paper proposes a widely applicable method and a mensurable formula for determining the µ11 constant of layer-dependent 2D materials with high precision. A combination of in situ micro-Raman spectroscopy and piezoresponse force microscopy (PFM) imaging was used to quantify the strain distribution and effective out-of-plane electromechanical coupling, respectively, for µ11 constant calculation. The µ11 constants and their physical correlation with the variable mechanical conditions of naturally bent structures have been obtained extensively for the representative mono-to-few layered MX2 family (M = W and Mo; X = S and Se), and the result is perfectly consistent with the estimated order-of-magnitude of the µ11 value (about 0.065) of monolayer MoS2. The quantification of the flexoelectric constant in this work not only promotes the understanding of mechanical and electromechanical properties in van der Waals materials, but also paves the way for developing novel 2D nano-energy devices and mechanical transducers based on flexoelectric effects.

Tunable lattice dynamics and dielectric functions of two-dimensional Bi2O2Se: striking layer and temperature dependent effects.

Two-dimensional (2D) Bi2O2Se semiconductors with a narrow band gap and ultrahigh mobility have been regarded as an emerging candidate for optoelectronic devices, whereas the ambiguous phonon characteristics and optical properties still limit their future applications. Herein, high-quality centimeter-scale 2D Bi2O2Se films are successfully synthesized to disclose the lattice dynamics and dielectric functions under the control of thickness and temperature. It has been demonstrated that the stronger electrostatic Bi-Se interactions result in a stiffened phonon vibration of thicker Bi2O2Se layers. Three excitons (Ea, Eb, and Ec) exhibit significant red shifts with layer stacking. Interestingly, the dielectric properties in the visible-near infrared region (Ea and Eb) are dominated by the combined effect of the joint density of states and mass density, whereas the dielectric properties in the ultraviolet region (Ec) are dominated by the exciton effect. Furthermore, the temperature-sensitivity of the phonon frequency and exciton transition energies is revealed to be layer-dependent. In particular, the optical response of Eb excitons exhibits a prominent dependence on temperature, which indicates a promising optical modulation by temperature in the visible spectrum. This study enriches the knowledge about phonon dynamics and dielectric properties for 2D Bi2O2Se, which provides an essential reference for high-performance related optoelectronic devices.

Optically Induced Multistage Phase Transition in Coherent Phonon-Dominated a-GeTe.

Ultrafast photoexcitation can decouple the multilevel nonequilibrium dynamics of electron-lattice interactions, providing an ideal probe for dissecting photoinduced phase transition in solids. Here, real-time time-dependent density functional theory simulations combined with occupation-constrained DFT methods are employed to explore the nonadiabatic paths of optically excited a-GeTe. Results show that the short-wavelength ultrafast laser is capable of generating full-domain carrier excitation and repopulation, whereas the long-wavelength ultrafast laser favors the excitation of lone pair electrons in the antibonded state. Photodoping makes the double-valley potential energy surface shallower and allows the insertion of A1g coherent forces in the atomic pairs, by which the phase reversal of Ge and Te atoms in the ⟨001⟩ direction is activated with ultrafast suppression of the Peierls distortion. These findings have far-reaching implications regarding nonequilibrium phase engineering strategies based on phase-change materials.

A polar-switchable and controllable negative phototransistor for information encryption.

Anomalous negative phototransistors have emerged as a distinct research area, characterized by a decrease in channel current under light illumination. Recently, their potential applications have been expanded beyond photodetection. Despite the considerable attention given to negative phototransistors, negative photoconductance (NPC) in particular remains relatively unexplored, with limited research advancements as compared to well-established positive phototransistors. In this study, we designed ferroelectric field-effect transistors (FeFETs) based on the WSe2/CIPS van der Waals (vdW) vertical heterostructures with a buried-gated architecture. The transistor exhibits NPC and positive photoconductance (PPC), demonstrating the significant role of ferroelectric polarization in the distinctive photoresponse. The observed inverse photoconductance can be attributed to the dynamic switching of ferroelectric polarization and interfacial charge transfer processes, which have been investigated experimentally and theoretically using Density Functional Theory (DFT). The unique phenomena enable the coexistence of controllable and polarity-switchable PPC and NPC. The novel feature holds tremendous potential for applications in optical encryption, where the specific gate voltages and light can serve as universal keys to achieve modulation of conductivity. The ability to manipulate conductivity in response to optical stimuli opens up new avenues for developing secure communication systems and data storage technologies. Harnessing this feature enables the design of advanced encryption schemes that rely on the unique properties of our material system. The study not only advances the development of NPC but also paves the way for more robust and efficient methods of optical encryption, ensuring the confidentiality and integrity of critical information in various domains, including data transmission, and information security.

Ultrabroadband Tellurium Photoelectric Detector from Visible to Millimeter Wave.

Ultrabroadband photodetection is of great significance in numerous cutting-edge technologies including imaging, communications, and medicine. However, since photon detectors are selective in wavelength and thermal detectors are slow in response, developing high performance and ultrabroadband photodetectors is extremely difficult. Herein, one demonstrates an ultrabroadband photoelectric detector covering visible, infrared, terahertz, and millimeter wave simultaneously based on single metal-Te-metal structure. Through the two kinds of photoelectric effect synergy of photoexcited electron-hole pairs and electromagnetic induced well effect, the detector achieves the responsivities of 0.793 A W-1 at 635 nm, 9.38 A W-1 at 1550 nm, 9.83 A W-1 at 0.305 THz, 24.8 A W-1 at 0.250 THz, 87.8 A W-1 at 0.172 THz, and 986 A W-1 at 0.022 THz, respectively. It also exhibits excellent polarization detection with a dichroic ratio of 468. The excellent performance of the detector is further verified by high-resolution imaging experiments. Finally, the high stability of the detector is tested by long-term deposition in air and high-temperature aging. The strategy provides a recipe to achieve ultrabroadband photodetection with high sensitivity and fast response utilizing full photoelectric effect.

Designing Monoclinic Heterophase Coexistence for the Enhanced Piezoelectric Performance in Ternary Lead-Based Relaxor Ferroelectrics.

Enhanced piezoelectric, dielectric properties and thermal stability in ternary relaxor-PbTiO3 based ferroelectric crystals are expected to develop the next-generation of electromechanical devices. However, due to their increased disorder compared to other ferroelectrics, designing a controllable phase boundary structure and engineered domain remains a challenging task. Here, we construct a monoclinic heterophase coexisting in a ternary Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystal with optimized composition and an ultrahigh piezoelectric coefficient of 1400 pC N-1, to quantify the correlation between spontaneous nanopolarity and phase heterogeneity, in an attempt to understand the origin of the exceptional functionalities. By designing an in situ high-resolution spectroscopic-microscopic technique, we have observed Ma and Mc heterophase mixtures spatially separated by the monoclinic heterophase boundary (MHB), which are responsible for the ferroelectric-dominated and relaxor-ferroelectric-dominated nanodomain structure, respectively. Internal energy mapping from optical soft mode dynamics reveals the inhomogeneous polarization and local symmetry on both sides of the MHB. Various molecular polarizabilities and localized octahedral distortions correlate directly with monoclinic regions and electromechanical contribution. This work clarifies the heterogeneity between structure, energy, and polar order and provides a new design freedom for advanced relaxor ferroelectrics.

Ultrathin Fe-ReS2 Nanosheets as Electrocatalysts for Accelerating Sulfur Reduction in Li-S Batteries.

Lithium-sulfur batteries are promising next-generation energy storage systems with high theoretical specific capacity. Despite extensive research efforts, it is still challenging to rationally design electrocatalysts with fast kinetics and effective adsorption of polysulfides. Herein, Fe-doped ReS2 (Fe-ReS2) ultrathin nanosheets are prepared as an electrocatalyst to trap the intermediates and accelerate the sulfur reduction reaction kinetics. Density functional theory calculations combined with activation energies in the multistep sulfur reduction reaction reveal that the Fe-ReS2 considerably reduces the activation energy and optimizes the optimum adsorption strength of polysulfides and catalytic activity. The Fe-ReS2/S exhibits a highly reversible discharge capacity of 882.3 mA h g-1 at 1 C. For 500 cycles, the capacity fade rate is 0.013% per cycle. Moreover, in situ Raman spectroscopy measurements further confirmed that both sulfur reduction and oxidation processes were significantly enhanced by Fe-ReS2.

Ultra-Stable, Endurable, and Flexible Sb2TexSe3-x Phase Change Devices for Memory Application and Wearable Electronics.

Flexible memory and wearable electronics represent an emerging technology, thanks to their reliability, compatibility, and superior performance. Here, an Sb2TexSe3-x (STSe) phase change material was grown on flexible mica, which not only exhibited superior nature in thermal stability for phase change memory application but also revealed novel function performance in wearable electronics, thanks to its excellent mechanical reliability and endurance. The thermal stability of Sb2Te3 was improved obviously with the crystallization temperature elevated 60 K after Se doping, for the enhanced charge localization and stronger bonding energy, which was validated by the Vienna ab initio simulation package calculations. Based on the ultra-stability of STSe, the STSe-based phase change memory shows 65 000 reversible phase change ability. Moreover, the assembled flexible device can show real-time monitoring and recoverability response in sensing human activities in different parts of the body, which proves its effective reusability and potential as wearable electronics. Most importantly, the STSe device presents remarkable working reliability, reflected by excellent endurance over 100 s and long retention over 100 h. These results paved a novel way to utilize STSe phase change materials for flexible memory and wearable electronics with extreme thermal and mechanical stability and brilliant performance.

Silver/silver halide supported on mesoporous ceria particles and photo-CWPO degradation under visible light for organic compounds in acrylonitrile wastewater.

Silver/silver halide supported on ordered mesoporous ceria particles (Ag/AgCl/CeO2) were rapidly prepared by microwave-assisted soft template method, deposition precipitation method and photoreduction method, using cerium nitrate and silver nitrate as raw materials and block copolymer F127 as a template. The morphology, structure and chemical composition of the catalyst were characterized by XRD, SEM, EDS, TEM, N2 adsorption-desorption and UV-Vis Drs. Catalytic wet peroxide system assisted with visible light photocatalysis (photo-CWPO) was conducted to investigate the performance of organics degradation by Ag/AgCl/CeO2 as a catalyst in acrylonitrile wastewater. The results showed that the Ag/AgCl/CeO2 prepared has an ordered mesoporous structure, Ag and AgCl are formed on the surface of CeO2, with a specific surface area of 302.6-336.2 m2 g-1 and the average pore size is 8.04-8.90 nm. There is a strong absorption in the visible region and a band gap of 2.9 eV. The Ag/AgCl/CeO2 catalyst has higher catalytic performance in the photo-CWPO system than in the CWPO system alone. Ag loading, catalyst and H2O2 dosage, and pH value can affect the COD removal. When the concentration of COD in acrylonitrile wastewater was 500 mg L-1, the amount of catalyst was 200 mg, the amount of H2O2 (30%) was 8 mL, and the reaction time was 60 min, the COD removal reached 90%.

Thermal Conductivity of Large-Area Polycrystalline MoSe2 Films Grown by Chemical Vapor Deposition.

It is of great importance to understand the thermal properties of MoSe2 films for electronic and optoelectronic applications. In this work, large-area polycrystalline MoSe2 films are prepared using a low-cost, controllable, large-scale, and repeatable chemical vapor deposition method, which facilitates direct device fabrication. Raman spectra and X-ray diffraction patterns indicate a hexagonal (2H) crystal structure of the MoSe2 film. Ellipsometric spectra analysis indicates that the optical band gap of the MoSe2 film is estimated to be ∼1.23 eV. From the analysis of the temperature-dependent and laser-power-dependent Raman spectra, the thermal conductivity of the suspended MoSe2 films is found to be ∼28.48 W/(m·K) at room temperature. The results can provide useful guidance for an effective thermal management of large-area polycrystalline MoSe2-based electronic and optoelectronic devices.