Liquid‐Exfoliated Black Phosphorous Nanosheet Thin Films for Flexible Resistive Random Access Memory Applications

Black phosphorous (BP) is a unique layered p‐type semiconducting material. The successful use of BP nanosheets in field‐effect transistors fueled research on BP atomic layers that focuses on, e.g., the exploration of their optical and electronic properties, and promising applications in (opto)electronics. However, BP films are prone to degradation in ambient conditions, which prevents their commercial application. Here, a route to the application of BP films as an environmental stable nonvolatile resistive random access memory is presented. The BP films, which are prepared from exfoliated BP nanosheets in selected solvents, show solvent‐dependent degradation upon ambient exposure, inducing the formation of an amorphous top degraded layer (TDL). The TDL acts as an insulating barrier just below the Al electrode. This property that was only obtained by degradation, confers a bipolar resistive switching behavior with a high ON/OFF current ratio up to ~3 × 10⁵ and excellent retention ability over 10⁵ s to the flexible BP memory devices. The TDL also prevents propagation of degradation further into the film, ensuring excellent memory performance even after three month of ambient exposure.     

Dual Functionalization of Liquid‐Exfoliated Semiconducting 2H‐MoS2 with Lanthanide Complexes Bearing Magnetic and Luminescence Properties

Liquid exfoliated, atomically thin semiconducting transition metal dichalcogenides (TMDs), as inorganic equivalents of graphene, have attracted great interest due to their distinctive physical, optoelectronic, and chemical properties. Functionalization of 2D TMDs brings new prospects for applications in optoelectronics, quantum technologies, catalysis, and medicine. In this report, dual functionalization of 2D semiconducting 2H‐MoS₂ nanosheets through simultaneous incorporation of magnetic and luminescent properties is demonstrated. A facile method is proposed for tuning the properties of the TDM semiconductors and accessing multimodal platforms, consisting in covalent grafting of lanthanide complexes onto the surface of 2D TMDs. Dual functionalization of liquid‐exfoliated MoS₂ nanosheets is demonstrated simultaneously with both europium (III) and gadolinium (III) complexes to form a colloidally stable luminescent (with millisecond lifetimes) and paramagnetic MoS₂‐based nanohybrid material. This work is the first example of transition metal dichalcogenide nanosheets functionalized with preformed lanthanide complexes. These findings open new prospects for covalent functionalization of TMDs with molecular species bearing specific functionalities as a means to tune the optoelectronic properties of the semiconductors, in order to create advanced materials and devices with a wide range of functionalities.     

Ionic Liquid–Polymer Composites: A New Platform for Multifunctional Applications

Ionic liquids (ILs) have emerged as a novel class of chemical compounds for the development of advanced (multi)functional materials with outstanding potential in applications of several areas due to their unique properties and functionalities. The combination of ILs with polymers, in a composite, allows for developing smart materials, which synergistically combine the features of specific polymers and ILs. Moreover, ILs can be extensively modified by the incorporation of functional groups with specific properties into the cation, anion, or both. Thus, it is possible to tune the IL, the polymer, or both to obtain a broad spectrum of multifunctional composites and address the specific requirements of many applications. This work focusses on advanced materials and strategies concerning ILs and polymers for the development of smart IL/polymer‐based materials for applications including responsive and sensitive sensors, actuators, environment, batteries, fuel cells, and biomedical applications.     

Performances of Liquid‐Exfoliated Transition Metal Dichalcogenides as Hole Injection Layers in Organic Light‐Emitting Diodes

2D transition metal dichalcogenide (TMD) nanosheets, including MoS₂, WS₂, and TaS₂, are used as hole injection layers (HILs) in organic light‐emitting diodes (OLEDs). MoS₂, WS₂, and TaS₂ nanosheets are prepared using an exfoliation by ultrasonication method. The thicknesses and sizes of the TMD nanosheets are measured to be 3.1–4.3 nm and more than 100 nm, respectively. The work functions of the TMD nanosheets increase from 4.4–4.9 to 4.9–5.1 eV following ultraviolet/ozone (UVO) treatment. The turn‐on voltages at 10 cd m^?2 for UVO‐treated TMD‐based devices decrease from 7.3–12.8 to 4.3–4.4 V and maximum luminance efficiencies increase from 5.74–9.04 to 12.01–12.66 cd A^?1. In addition, this study confirms that the stabilities of the devices in air can be prolonged by using UVO‐treated TMDs as HILs in OLEDs. These results demonstrate the great potential of liquid‐exfoliated TMD nanosheets for use as HILs in OLEDs.     

Metallic 1T‐WS2 for Selective Impedimetric Vapor Sensing

Selective gas sensing is of immense importance for industrial as well as safety purposes. Here it is shown that metallic 1T phase transition metal dichalcogenides, such as tungsten sulfide (WS₂), provide sensitive and selective platform for gas sensing. Using impedance spectroscopy distinguishable alterations can be detected on the impedance phase spectrum of interdigitated gold electrode modified with chemically exfoliated 1T‐WS₂ caused by different vapors. In particular, it is found that the impedance phase spectra of 1T‐WS₂ device present different resonant frequencies with maximum around 1 Hz in the presence of methanol vapor and around 1 kHz in the presence of water vapor. Such a well‐distinguished signal allows their selective detection also when they are present in a mixture. The impedance phase spectra allow the selective methanol and water vapor sensing with an impedimetric device based on 1T‐WS₂. This system utilizing 1T phase of WS₂ for selective gas sensing based on impedance spectroscopy opens new avenues for gas sensing and shall find wide spectra of applications.     

1T‐Phase WS2 Protein‐Based Biosensor

Metallic 1T‐phase transition metal dichalcogenides have been recognized for their desirable properties like high surface‐to‐volume ratio, high conductivity, and capacitive behavior, making them outstanding for catalytic and sensing applications. Herein, a hydrogen peroxide (H₂O₂) biosensor is constructed by the immobilization of hemoglobin (Hb) on 1T‐phase WS₂ (1T‐WS₂) sheets, and entrapment by glutaraldehyde. 1T‐WS₂ not only displays electrocatalytic activity toward the reduction of H₂O₂ but also provides a high surface‐to‐volume ratio and conductive platform for the immobilization of Hb and facilitation of its electron transfer to the electrode surface. The advantageous role of 1T‐phase WS₂ is further demonstrated for the construction of a heme‐based H₂O₂ biosensor compared to its 1T‐phase MoS_2, MoSe₂, and WSe₂ counterparts. Synergistic interactions between 1T‐WS₂ and Hb result in a H₂O₂ biosensor with high analytical performance in terms of wide range, sensitivity, selectivity, reproducibility, repeatability, and stability. These findings have profound impact in the research fields of electrochemical sensing and biodiagnostics.     

Precise Single‐Step Electrophoretic Multi‐Sized Fractionation of Liquid‐Exfoliated Nanosheets

Transition metal dichalcogenides (TMDs) 2D nanomaterials' integration into the industry has been hampered by the ability to mass produce nanosheets of designed sizes. Large‐scale exfoliation is possible with liquid‐phase exfoliation, but precise subsequent isolation of a specified size dimension has yet to be realized. Herein, a precise and efficient method for both size fractionation and nanosheet retrieval is demonstrated using electrophoretic isolation of MoS₂ nanosheets in low melting agarose. This can be applied to find out the relative size distribution and sizes within a sample of MoS₂. Fractionation can be estimated visually by the relative spread of sizes based on their banding within the agarose. The additional degrees of freedom conferred by the agarose allow for more precise design and control over the size selection process. This serves as a quick and easy method of discerning and isolating the desired size range of MoS₂ for further downstream applications in a single step. Nanosheets separated by the procedure retain their structural properties and display size dependency shown empirically and theoretically. This technique is versatile and can be varied according to the needs. It may truly bring large‐scale isolation that much needed step closer to industrial scale production.     

van der Waals Epitaxial Growth of Atomically Thin 2D Metals on Dangling‐Bond‐Free WSe2 and WS2

2D metals have attracted considerable recent attention for their special physical properties, such as charge density waves, magnetism, and superconductivity. However, despite some recent efforts, the synthesis of ultrathin 2D metals nanosheets down to monolayer thickness remains a significant challenge. Herein, by using atomically flat 2D WSe₂ or WS₂ as the growth substrate, the synthesis of atomically thin 2D metallic MTe₂ (M = V, Nb, Ta) single crystals with the thickness down to the monolayer regime and the creation of atomically thin MTe₂/WSe₂ (WS₂) vertical heterojunctions is reported. Comparison with the growth on the SiO₂/Si substrate under the same conditions reveals that the utilization of the dangling‐bond‐free WSe₂ or WS₂ as the van der Waals epitaxy substrates is crucial for the successful realization of atomically thin MTe₂ (M = V, Nb, Ta) nanosheets. It is further shown that the epitaxial grown 2D metals can function as van der Waals contacts for 2D semiconductors with little interface damage and improved electronic performance. This study defines a robust van der Waals epitaxy pathway to ultrathin 2D metals, which is essential for fundamental studies and potential technological applications of this new class of materials at the 2D limit.     

Enhanced Photorefractivity of Poly(N‐vinylcarbazole)‐Based Composites through Electric‐Field Treatments and Ionic Liquid Doping

It is shown that the photorefractive (PR) performance of polymer composites based on poly(N‐vinylcarbazole) can be improved when samples are subjected to an electric field for a certain time, i.e. conditioned, previous to the PR characterization. It is also found that for conditioned samples the addition of an organic ionic liquid to the PR composition allows to obtain PR effect without the need of using a sensitizer. The typical electric field treatment time at room temperature and at a field of 20 V µm^?1 is 20 min. This procedure leads to a decrease of dark conductivity and an increase of photoconductivity, and consequently an increase of conductivity contrast. This results in higher PR two‐beam‐coupling gain coefficients and shorter response times, particularly at low fields. Dependencies of the process dynamics on impurities, applied field strength, temperature and the presence of an organic ionic liquid are examined in detail. It is remarkable the significant increase of the PR gain coefficients, and more drastically of the net gain coefficients, observed at low fields (<55 V µm^?1), when an ionic organic liquid such as benzalkonium chloride is added to unsensitized conditioned PR composites. These findings open a new route to improve the PR performance, not only of PVK‐based composites, but also of other types of organic materials, the main advantage being that no sensitizer is needed.     

Few‐Layered WS2 Nanoplates Confined in Co,N‐Doped Hollow Carbon Nanocages: Abundant WS2 Edges for Highly Sensitive Gas Sensors

Edges of 2D transition metal dichalcogenides (TMDs) are well known as highly reactive sites, thus researchers have attempted to maximize the edge site density of 2D TMDs. In this work, metal‐organic framework (MOF) templates are introduced to synthesize few‐layered WS₂ nanoplates (a lateral dimension of ≈10 nm) confined in Co, N‐doped hollow carbon nanocages (WS₂_Co‐N‐HCNCs), for highly sensitive NO₂ gas sensors. WS₂ precursors are assembled in the surface cavity of Co‐based zeolite imidazole framework (ZIF‐67) and subsequent pyrolysis produced WS₂_Co‐N‐HCNCs. During the pyrolysis, the carbonized ZIF‐67 are doped by Co and N elements, and the growth of WS₂ is effectively suppressed, creating few‐layered WS₂ nanoplates functionalized Co‐N‐HCNCs. The WS₂_Co‐N‐HCNCs exhibit outstanding NO₂ sensing characteristics at room temperature, in terms of response (48.2% to 5 ppm), selectivity, response and recovery speed, and detection limit (100 ppb). These results are attributed to the enhanced adsorption and desorption kinetics of NO₂ on abundant WS₂ edges, confined in the gas permeable HCNCs. This work opens up an efficient way for the facile synthesis of edge abundant few‐layered TMDs combined with porous carbon matrix via MOF templating route, for applications relying on highly active sites.     

Room‐Temperature Self‐Healing and Recyclable Tough Polymer Composites Using Nitrogen‐Coordinated Boroxines

In this paper, nitrogen‐coordinated boroxines are exploited for the fabrication of self‐healing and recyclable polymer composites with enhanced mechanical properties. The 3D polymer networks cross‐linked with nitrogen‐coordinated boroxines are first synthesized through the trimerization of ortho‐aminomethyl‐phenylboronic acid groups at the terminals of poly(propylene glycol) (PPG) chains, and subsequently, the mechanically robust polymer composites are fabricated by utilizing the complexation of nitrogen‐coordinated boroxine‐containing PPG (N‐boroxine‐PPG) with poly(acrylic acid) (PAA) and hydrogen‐bonding interactions between them. The N‐boroxine‐PPG is soft with a tensile strength of 0.19 MPa, whereas the tensile strengths of N‐boroxine‐PPG/PAA composites can be tailored to range from 1.7 to 12.7 MPa by increasing the PAA contents in the polymer composites. It is revealed that the amine ligands can facilitate the formation and dissociation of nitrogen‐coordinated boroxines at room temperature. Moreover, the reversibility of nitrogen‐coordinated boroxines and hydrogen‐bonding interactions enable multiple cycles of healing and recycling of the damaged N‐boroxine‐PPG/PAA composites. The healed and recycled N‐boroxine‐PPG/PAA polymer composites regain most of their mechanical strength.     

Exfoliated Layered Manganese Trichalcogenide Phosphite (MnPX3, X = S,Se) as Electrocatalytic van der Waals Materials for Hydrogen Evolution

Layered metal trichalcogen phosphites, also entitled as metal phosphorus chalcogenides (MPX₃), have regained abundant interest, not only due to their magnetic properties, but also due to promising performances in energy storage and conversion. Herein, two different layered manganese trichalcogen phosphites, MnPX₃ (X = S, Se), are synthetized and submitted to shear force exfoliation. Structural and morphological characterization point to the fact that exfoliated MPX₃ (exf‐MnPX₃) undergo mainly a downsizing process, alongside with delamination. Layered exf‐MnPSe₃ has the lowest onset potential for hydrogen evolution reaction (HER) in both media. In acidic media, a comparative improvement of 350 mV is observed for exf‐MnPSe₃ relative to the bulk MnPSe₃. The materials stability as electrocatalysts is also tested for HER in a wide pH range, in which exf‐MnPSe₃ has a good stability after 100 cycles. The improved performance of exf‐MnPSe₃ can be correlated with the lower relative abundance of Mn and P oxides detected in the Mn 2p and P 2p core levels. Such materials show a great promise for future in a hydrogen‐based economy.     

Recent Progress on 2D Noble‐Transition‐Metal Dichalcogenides

Emerging classes of 2D noble‐transition‐metal dichalcogenides (NTMDs) stand out for their unique structure and novel physical properties in recent years. With the nearly full occupation of the d orbitals, 2D NTMDs are expected to be more attractive due to the unique interlayer vibrational behaviors and largely tunable electronic structures compared to most transition metal dichalcogenide semiconductors. The novel properties of 2D NTMDs have stimulated various applications in electronics, optoelectronics, catalysis, and sensors. Here, the latest development of 2D NTMDs are reviewed from the perspective of structure characterization, preparation, and application. Based on the recent research, the conclusions and outlook for these rising 2D NTMDs are presented.     

Direct and Indirect Exciton Dynamics in Few‐Layered ReS2 Revealed by Photoluminescence and Pump‐Probe Spectroscopy

Atomically thin‐layered ReS₂ with a distorted 1T structure has attracted attention because of its intriguing optical and electronic properties. Here, the direct and indirect exciton dynamics of a three‐layered ReS₂ is investigated by polarization‐resolved transient photoluminescence (PL) and ultrafast pump‐probe spectroscopy. The various time scales of the decay signals of the time‐resolved PL (<10 ps), with monitoring of the populations of electron–hole pairs (exciton), and the transient differential reflectance (≈1 and 100 ps), with monitoring of the populations of electrons and/or holes in the excited states, are observed. These results reveal the characteristic exciton dynamics: rapid relaxation of direct excitons (electron–hole pairs) and slow relaxation of the momentum‐mismatched indirect excitons accompanied by a one‐phonon emission process. These findings provide important information regarding the indirect bandgap nature of few‐layered ReS₂ and its characteristic exciton dynamics, boosting the understanding of the novel electronic and optical properties of atomically thin‐layered ReS₂.     

Sub‐Millimeter‐Scale Monolayer p‐Type H‐Phase VS2

2D H‐phase vanadium disulfide (VS₂) is expected to exhibit tunable semiconductor properties as compared with its metallic T‐phase structure, and thus is of promise for future electronic applications. However, to date such 2D H‐phase VS₂ nanostructures have not been realized in experiment likely due to the polymorphs of vanadium sulfides and thermodynamic instability of H‐phase VS₂. Preparation of H‐phase VS₂ monolayer with lateral size up to 250 µm, as a new member in the 2D transition metal dichalcogenides (TMDs) family, is reported. A unique growth environment is built by introducing the molten salt‐mediated precursor system as well as the epitaxial mica growth platform, which successfully overcomes the aforementioned growth challenges and enables the evolution of 2D H‐phase structure of VS₂. The honeycomb‐like structure of H‐phase VS₂ with broken inversion symmetry is confirmed by spherical aberration‐corrected scanning transmission electron microscopy and second harmonic generation characterization. The phase structure is found to be ultra‐stable up to 500 K. The field‐effect device study further demonstrates the p‐type semiconducting nature of the 2D H‐phase VS₂. The study introduces a new phase‐stable 2D TMDs materials with potential features for future electronic devices.     

Production and Patterning of Liquid Phase–Exfoliated 2D Sheets for Applications in Optoelectronics

2D materials (2DMs), which can be produced by exfoliating bulk crystals of layered materials, display unique optical and electrical properties, making them attractive components for a wide range of technological applications. This review describes the most recent developments in the production of high‐quality 2DMs based inks using liquid‐phase exfoliation (LPE), combined with the patterning approaches, highlighting convenient and effective methods for generating materials and films with controlled thicknesses down to the atomic scale. Different processing strategies that can be employed to deposit the produced inks as patterns and functional thin‐films are introduced, by focusing on those that can be easily translated to the industrial scale such as coating, spraying, and various printing technologies. By providing insight into the multiscale analyses of numerous physical and chemical properties of these functional films and patterns, with a specific focus on their extraordinary electronic characteristics, this review offers the readers crucial information for a profound understanding of the fundamental properties of these patterned surfaces as the millstone toward the generation of novel multifunctional devices. Finally, the challenges and opportunities associated to the 2DMs' integration into working opto‐electronic (nano)devices is discussed.     

Role of Molecular Sieves in the CVD Synthesis of Large‐Area 2D MoTe2

The synthesis of high‐quality 2D MoTe₂ with a desired phase on SiO₂/Si substrate is crucial to its diverse applications. A side reaction of Te with the substrate Si leading to SiTe and Si₂Te₃ tends to happen during growth, resulting in the failure to obtain MoTe₂. It has been found that molecular sieves can adsorb the silicon telluride byproducts and eliminate the influence of the side reaction during the chemical vapor deposition synthesis of MoTe₂. With the help of molecular sieves, few‐layer 1T′ MoTe₂ can be grown from the MoO_x precursor. Pure 1T′ MoTe₂ and 2H MoTe₂ regions in centimeter‐sized areas synthesized on the same piece of SiO₂/Si substrate can be obtained by using an overlapped geometry. The strategy provides a new method to controllably synthesize MoTe₂ with desired phases and can be generalizable to the synthesis of other tellurium‐based layered materials.