Light-Induced Tunable Ferroelectric Polarization in Dipole-Embedded Metal-Organic Framework.

Reversible regulation of ferroelectric polarization possesses great potentials recently in bionic neural networks. Photoinduced cis-trans isomers have changeable dipole moments, but they cannot be directed to some specific orientation. Here, we construct a host-guest composite structure which consists of a porous ferroelectric metal (Ni)-organic framework [Ni(DPA)2] as host and photoisomer, azobenzene (AZB), as guest molecules. When AZB molecules are embedded in the nanopores of Ni(DPA)2 in the form of a single molecule, polarization strength tunable regulation is realized after ultraviolet irradiation of 365 and 405 nm via cis-trans isomerism transformation of AZB. An intrinsic built-in field originating from the distorted {NiN2O4} octahedra in Ni(DPA)2 directs the dipole moments of AZB to the applied electric field. As a result, the overlapped ferroelectric polarization strength changes with content of cis-AZB after ultraviolet and visible irradiation. Such a connection of ferroelectric Ni(DPA)2 structure with cis-trans isomers provides an important strategy for regulating the ferroelectric polarization strength.

Reversible engineering of topological insulator surface state conductivity through optical excitation.

Despite the broadband response, limited optical absorption at a particular wavelength hinders the development of optoelectronics based on Dirac fermions. Heterostructures of graphene and various semiconductors have been explored for this purpose, while non-ideal interfaces often limit the performance. The topological insulator (TI) is a natural hybrid system, with the surface states hosting high-mobility Dirac fermions and the small-bandgap semiconducting bulk state strongly absorbing light. In this work, we show a large photocurrent response from a field effect transistor device based on intrinsic TI Sn-Bi1.1Sb0.9Te2S (Sn-BSTS). The photocurrent response is non-volatile and sensitively depends on the initial Fermi energy of the surface state, and it can be erased by controlling the gate voltage. Our observations can be explained with a remote photo-doping mechanism, in which the light excites the defects in the bulk and frees the localized carriers to the surface state. This photodoping modulates the surface state conductivity without compromising the mobility, and it also significantly modify the quantum Hall effect of the surface state. Our work thus illustrates a route to reversibly manipulate the surface states through optical excitation, shedding light into utilizing topological surface states for quantum optoelectronics.

Raman fingerprint of aligned graphene/h-BN superlattices.

Graphene placed on hexagonal-boron nitride (h-BN) experiences a superlattice (Moiré) potential, which leads to a strong reconstruction of graphene's electronic spectrum with new Dirac points emerging at sub-eV energies. Here we study the effect of such superlattices on graphene's Raman spectrum. In particular, the 2D Raman peak is found to be exquisitely sensitive to the misalignment between graphene and h-BN lattices, probably due to the presence of a strain distribution with the same periodicity of the Moiré potential. This feature can be used to identify graphene superlattices with a misalignment angle smaller than 2°.

Strongly coupled magneto-exciton condensates in large-angle twisted double bilayer graphene.

Excitons, pairs of electrons and holes, undergo a Bose-Einstein condensation at low temperatures. An important platform to study excitons is double-layer two-dimensional electron gases, with two parallel planes of electrons and holes separated by a thin insulating layer. Lowering this separation (d) strengthens the exciton binding energy, however, leads to the undesired interlayer tunneling, resulting in annihilation of excitons. Here, we report the observation of a sequences of robust exciton condensates (ECs) in double bilayer graphene twisted to ~ 10° with no insulating mid-layer. The large momentum mismatch between two graphene layers suppresses interlayer tunneling, reaching a d ~ 0.334 nm. Measuring the bulk and edge transport, we find incompressible states corresponding to ECs when both layers are in half-filled N = 0, 1 Landau levels (LLs). Theoretical calculations suggest that the low-energy charged excitation of ECs can be meron-antimeron or particle-hole pair, which relies on both LL index and carrier type. Our results establish a novel platform with extreme coupling strength for studying quantum bosonic phase.

Robust Weak Antilocalization Effect Up to ∼120 K in the van der Waals Crystal Fe5-xGeTe2 with Near-Room-Temperature Ferromagnetism.

The van der Waals Fe5-xGeTe2 is a 3d ferromagnetic metal with a high Curie temperature of 275 K. We report herein the observation of an exceptional weak antilocalization (WAL) effect that can persist up to 120 K in an Fe5-xGeTe2 nanoflake, indicating the dual nature with both itinerant and localized magnetism of 3d electrons. The WAL behavior is characterized by the magnetoconductance peak around zero magnetic field and is supported by the calculated localized nondispersive flat band around the Fermi level. The peak to dip crossover starting around 60 K in magnetoconductance is visible, which could be ascribed to temperature-induced changes in Fe magnetic moments and the coupled electronic band structure as revealed by angle-resolved photoemission spectroscopy and first-principles calculations. Our findings would be instructive for understanding the magnetic exchanges in transition metal magnets as well as for the design of next-generation room-temperature spintronic devices.

PDMS-Encapsulated MXene@Polyester Fabric Strain Sensor for Multifunctional Sensing Applications.

Flexible strain sensors based on 2D materials have been proven effective for wearable health monitoring devices, human motion detection, and fitness applications. These sensors are flexible, light, and user-friendly, but their sensitivity and detection range need to be enhanced. Among many 2D materials, MXene attracts much interest due to its remarkable properties, such as high electrical conductivity, excellent mechanical properties, flexibility, and good hydrophilicity. However, it is a challenge to fabricate strain sensors with extreme sensitivity and a wide sensing range. In this work, a multifunctional, cost-effective, and highly sensitive PDMS-encapsulated MXene@polyester fabric strain sensor was fabricated. Firstly, complete adsorption of MXene within the fabric formed conductive networks, and then PDMS was used to endow superhydrophobicity and corrosion resistance. The strain sensor demonstrated multifunctional applications and outstanding performance, such as long-term stability (over 500 cycles) and a wide sensing range (8%). The proposed sensor has promising potential for wearable electronic devices such as health monitoring systems and physiological sensing applications.

Ultrahigh Energy and Power Densities of d-MXene-Based Symmetric Supercapacitors.

Here, rational design electrodes are fabricated by mixing MXene with an aqueous solution of chloroauric acid (HAuCl4). In order to prevent MXene from self-restacking, the groups of -OH on the surface of Ti3C2Tx nanosheets underwent a one-step simultaneous self-reduction from AuCl4-, generating spaces for rapid ion transit. Additionally, by using this procedure, MXene's surface oxidation can be decreased while preserving its physio-chemical properties. The interlayered MX/Au NPs that have been obtained are combined into a conducting network structure that offers more active electrochemical sites and improved mass transfer at the electrode-electrolyte interface, both of which promote quick electron transfer during electrochemical reactions and excellent structural durability. The Ti3C2Tx-AuNPs film thus demonstrated a rate performance that was preferable to that of pure Ti3C2Tx film. According to the results of the characterization, the AuNPs effectively adorn the MXene nanosheets. Due to the renowned pseudocapacitance charge storage mechanism, MXene-based electrode materials also work well as supercapacitors in sulfuric acid, which is why MXene AuNPs electrodes have been tested in 3 M and 1 M H2SO4. The symmetric supercapacitors made of MXene and AuNPs have shown exceptional specific capacitance of 696.67 Fg-1 at 5 mVs-1 in 3 M H2SO4 electrolyte, and they can sustain 90% of their original capacitance for 5000 cycles. The highest energy and power density of this device, which operates within a 1.2 V potential window, are 138.4 Wh kg-1 and 2076 W kg-1, respectively. These findings offer a productive method for creating high-performance metal oxide-based symmetric capacitors and a straightforward, workable approach for improving MXene-based electrode designs, which can be applied to other electro-chemical systems that are ion transport-restricted, such as metal ion batteries and catalysis.

Next-generation graphene oxide additives composite membranes for emerging organic micropollutants removal: Separation, adsorption and degradation.

In the past two decades, membrane technology has attracted considerable interest as a viable and promising method for water purification. Emerging organic micropollutants (EOMPs) in wastewater have trace, persistent, highly variable quantities and types, develop hazardous intermediates and are diffusible. These primary issues affect EOMPs polluted wastewater on an industrial scale differently than in a lab, challenging membranes-based EOMP removal. Graphene oxide (GO) promises state-of-the-art membrane synthesis technologies and use in EOMPs removal systems due to its superior physicochemical, mechanical, and electrical qualities and high oxygen content. This critical review highlights the recent advancements in the synthesis of next-generation GO membranes with diverse membrane substrates such as ceramic, polyethersulfone (PES), and polyvinylidene fluoride (PVDF). The EOMPs removal efficiencies of GO membranes in filtration, adsorption (incorporated with metal, nanomaterial in biodegradable polymer and biomimetic membranes), and degradation (in catalytic, photo-Fenton, photocatalytic and electrocatalytic membranes) and corresponding removal mechanisms of different EOMPs are also depicted. GO-assisted water treatment strategies were further assessed by various influencing factors, including applied water flow mode and membrane properties (e.g., permeability, hydrophily, mechanical stability, and fouling). GO additive membranes showed better permeability, hydrophilicity, high water flux, and fouling resistance than pristine membranes. Likewise, degradation combined with filtration is two times more effective than alone, while crossflow mode improves the photocatalytic degradation performance of the system. GO integration in polymer membranes enhances their stability, facilitates photocatalytic processes, and gravity-driven GO membranes enable filtration of pollutants at low pressure, making membrane filtration more inexpensive. However, simultaneous removal of multiple contaminants with contrasting characteristics and variable efficiencies in different systems demands further optimization in GO-mediated membranes. This review concludes with identifying future critical research directions to promote research for determining the GO-assisted OMPs removal membrane technology nexus and maximizing this technique for industrial application.

Observation of ballistic avalanche phenomena in nanoscale vertical InSe/BP heterostructures.

Impact ionization, which supports carrier multiplication, is promising for applications in single photon detection1 and sharp threshold swing field effect devices2. However, initiating the impact ionization of avalanche breakdown requires a high applied electric field in a long active region, which hampers carrier multiplication with a high gain, low bias and superior noise performance3,4. Here we report the observation of ballistic avalanche phenomena in sub-mean free path (MFP) scaled vertical InSe/black phosphorus (BP)5-9 heterostructures10. We use these heterojunctions to fabricate avalanche photodetectors (APDs) with a sensitive mid-infrared light detection (4 µm wavelength) and impact ionization transistors with a steep subthreshold swing (<0.25 mV dec-1). The devices show a low avalanche threshold (<1 V), low noise figure and distinctive density spectral shape. Our transport measurements suggest that the breakdown originates from a ballistic avalanche phenomenon, where the sub-MFP BP channel support the lattice impact ionization by electrons and holes and the abrupt current amplification without scattering from the obstacles in a deterministic nature. Our results provide new strategies for the development of advanced photodetectors1,11,12 via efficient carrier manipulation at the nanoscale.

Enhanced performance of a graphene/GaAs self-driven near-infrared photodetector with upconversion nanoparticles.

Near-infrared photodetectors (NIRPDs) have attracted great attention because of their wide range of applications in many fields. Herein, a novel self-driven NIRPD at the wavelength of 980 nm is reported based on the graphene/GaAs heterostructure. Extraordinarily, its sensitivity to light illumination (980 nm) is far beyond the absorption limitation of GaAs (874 nm). This means that the photocurrent originates from the separation of photo-induced carriers in graphene, which is caused by the vertically built-in electric field formed through the high quality van der Waals contact between graphene and GaAs. Moreover, after introducing NaYF4:Yb3+/Er3+ upconversion nanoparticles (UCNPs) onto the graphene/GaAs heterojunction, the responsivity increases to be as superior as 5.97 mA W-1 and the corresponding detectivity is 1.1 × 1011 cm Hz0.5 W-1 under self-driven conditions. This dramatic improvement is mainly ascribed to the radiative energy transfer from UCNPs to the graphene/GaAs heterostructure. The high-quality and self-driven UCNPs/graphene/GaAs heterostructure NIRPD holds significant potential for practical application in low-consumption and large-scale optoelectronic devices.

Anomalous quantization trajectory and parity anomaly in Co cluster decorated BiSbTeSe2 nanodevices.

Dirac Fermions with different helicities exist on the top and bottom surfaces of topological insulators, offering a rare opportunity to break the degeneracy protected by the no-go theorem. Through the application of Co clusters, quantum Hall plateaus were modulated for the topological insulator BiSbTeSe2, allowing an optimized surface transport. Here, using renormalization group flow diagrams, we show the extraction of two sets of converging points in the conductivity tensor space, revealing that the top surface exhibits an anomalous quantization trajectory, while the bottom surface retains the 1/2 quantization. Co clusters are believed to induce a sizeable Zeeman gap ( > 4.8 meV) through antiferromagnetic exchange coupling, which delays the Landau level hybridization on the top surface for a moderate magnetic field. A quasi-half-integer plateau also appears at -7.2 Tesla. This allows us to study the interesting physics of parity anomaly, and paves the way for further studies simulating exotic particles in condensed matter physics.The topological surface states usually appear in pairs in a topological insulator, with one on the top surface and the other on the bottom surface. Here, Zhang et al. utilize Co cluster to induce a Zeeman gap on one surface through antiferromagnetic exchange coupling, and observe a quasi-half-integer plateau, suggesting the parity anomaly of Dirac fermions.

High electron mobility, quantum Hall effect and anomalous optical response in atomically thin InSe.

A decade of intense research on two-dimensional (2D) atomic crystals has revealed that their properties can differ greatly from those of the parent compound. These differences are governed by changes in the band structure due to quantum confinement and are most profound if the underlying lattice symmetry changes. Here we report a high-quality 2D electron gas in few-layer InSe encapsulated in hexagonal boron nitride under an inert atmosphere. Carrier mobilities are found to exceed 103 cm2 V-1 s-1 and 104 cm2 V-1 s-1 at room and liquid-helium temperatures, respectively, allowing the observation of the fully developed quantum Hall effect. The conduction electrons occupy a single 2D subband and have a small effective mass. Photoluminescence spectroscopy reveals that the bandgap increases by more than 0.5 eV with decreasing the thickness from bulk to bilayer InSe. The band-edge optical response vanishes in monolayer InSe, which is attributed to the monolayer's mirror-plane symmetry. Encapsulated 2D InSe expands the family of graphene-like semiconductors and, in terms of quality, is competitive with atomically thin dichalcogenides and black phosphorus.

Partial Oxidized Arsenene: Emerging Tunable Direct Bandgap Semiconductor.

Arsenene, as a member of the Group V elemental two-dimensional materials appears on the horizon, has shown great prospects. However, its indirect bandgap limits the applications in optoelectronics. In this theoretical work, we reported that partial oxidation can tune the indirect bandgap of arsenene into the direct one. Attributed to the enthalpy decreasing linear to the oxygen ratio, partial oxidized arsenene can be controllably produced by the progressive oxidation under low temperature. Importantly, by increasing the oxygen content from 1O/18As to 18O/18As, the oxidation can narrow the direct bandgap of oxidized arsenene from 1.29 to 0.02 eV. The bandgap of partial oxidized arsenene is proportional to the oxygen content. Consequently, the partial oxidized arsenene with tunable direct bandgap has great potentials in the high efficient infra light emitter and photo-voltaic devices.

Raman modes of MoS2 used as fingerprint of van der Waals interactions in 2-D crystal-based heterostructures.

In this work, we use Raman spectroscopy as a nondestructive and rapid technique for probing the van der Waals (vdW) forces acting between two atomically thin crystals, where one is a transition metal dichalcogenide (TMDC). In this work, MoS2 is used as a Raman probe: we show that its two Raman-active phonon modes can provide information on the interaction between the two crystals. In particular, the in-plane vibration (E2g(1)) provides information on the in-plane strain, while the out-of-plane mode (A1g) gives evidence for the quality of the interfacial contact. We show that a vdW contact with MoS2 is characterized by a blue shift of +2 cm(-1) of the A1g peak. In the case of a MoS2/graphene heterostructure, the vdW contact is also characterized by a shift of +14 cm(-1) of the 2D peak of graphene. Our approach offers a very simple, nondestructive, and fast method to characterize the quality of the interface of heterostructures containing atomically thick TMDC crystals.