Chemical Growth of 1T‐TaS2 Monolayer and Thin Films: Robust Charge Density Wave Transitions and High Bolometric Responsivity

Ultrathin two‐dimensional (2D) charge density wave (CDW) materials, with sharp resistance change at the phase‐transition temperature, yet with ultrathin thickness, hold great potential for electrical device applications. However, chemical synthesis of high‐quality samples and observation of the CDW states down to the monolayer limit is still of great challenge. Chemical vapor deposition of 1T‐TaS₂ sheets on hexagonal boron nitride (h‐BN) with robust CDW states even down to the monolayer extreme is reported here. Further, based on the near commensurate CDW to incommensurate CDW phase transition with a high temperature coefficient of resistance (TCR), highly responsive room‐temperature bolometers are fabricated by suspending the as‐grown 1T‐TaS₂ sheets.     

High Phase Purity of Large‐Sized 1T′‐MoS2 Monolayers with 2D Superconductivity

The development of transition metal dichalcogenides has greatly accelerated research in the 2D realm, especially for layered MoS₂. Crucially, the metallic MoS₂ monolayer is an ideal platform in which novel topological electronic states can emerge and also exhibits excellent energy conversion and storage properties. However, as its intrinsic metallic phase, little is known about the nature of 2D 1T′‐MoS₂, probably because of limited phase uniformity (<80%) and lateral size (usually <1 µm) in produced materials. Herein, solution processing to realize high phase‐purity 1T′‐MoS₂ monolayers with large lateral size is demonstrated. Direct chemical exfoliation of millimeter‐sized 1T′ crystal is introduced to successfully produce a high‐yield of 1T′‐MoS₂ monolayers with over 97% phase purity and unprecedentedly large size up to tens of micrometers. Furthermore, the large‐sized and high‐quality 1T′‐MoS₂ nanosheets exhibit clear intrinsic superconductivity among all thicknesses down to monolayer, accompanied by a slow drop of transition temperature from 6.1 to 3.0 K. Prominently, unconventional superconducting behavior with upper critical field far beyond the Pauli limit is observed in the centrosymmetric 1T′‐MoS₂ structure. The results open up an ideal approach to explore the properties of 2D metastable polymorphic materials.     

S‐Doped TiSe2 Nanoplates/Fe3O4 Nanoparticles Heterostructure

2D Sulfur‐doped TiSe₂/Fe₃O₄ (named as S‐TiSe₂/Fe₃O₄) heterostructures are synthesized successfully based on a facile oil phase process. The Fe₃O₄ nanoparticles, with an average size of 8 nm, grow uniformly on the surface of S‐doped TiSe₂ (named as S‐TiSe₂) nanoplates (300 nm in diameter and 15 nm in thickness). These heterostructures combine the advantages of both S‐TiSe₂ with good electrical conductivity and Fe₃O₄ with high theoretical Li storage capacity. As demonstrated potential applications for energy storage, the S‐TiSe₂/Fe₃O₄ heterostructures possess high reversible capacities (707.4 mAh g⁻¹ at 0.1 A g⁻¹ during the 100th cycle), excellent cycling stability (432.3 mAh g⁻¹ after 200 cycles at 5 A g⁻¹), and good rate capability (e.g., 301.7 mAh g⁻¹ at 20 A g⁻¹) in lithium‐ion batteries. As for sodium‐ion batteries, the S‐TiSe₂/Fe₃O₄ heterostructures also maintain reversible capacities of 402.3 mAh g⁻¹ at 0.1 A g⁻¹ after 100 cycles, and a high rate capacity of 203.3 mAh g⁻¹ at 4 A g⁻¹.     

Bismuthene Metallurgy: Transformation of Bismuth Particles to Ultrahigh‐Aspect‐Ratio 2D Microsheets

Ultrathin bismuth exhibits promising performance for topological insulators due to its narrow band gap and intrinsic strong spin–orbit coupling, as well as for energy‐related applications because of its electronic and mechanical properties. However, large‐scale production of 2D sheets via liquid‐phase exfoliation as an established large‐scale method is restricted by the strong interaction between bismuth layers. Here, a sonication method is utilized to produce ultrahigh‐aspect‐ratio bismuthene microsheets. The studies on the mechanism excludes the exfoliation of the layered bulk bismuth and formation of the microsheets is attributed to the melting of spherical particles (r = 1.5 µm) at a high temperature—generated under the ultrasonic tip—followed by a recrystallization step producing uniformly‐shaped ultrathin microsheets (A = 0.5–2 µm², t: ≈2 nm). Notably, although the preparation is performed in oxygenated aqueous solution, the sheets are not oxidized, and they are stable under ambient conditions for at least 1 month. The microsheets are used to construct a vapor sensor using electrochemical impedance spectroscopy as detection technique. The device is highly selective, and it shows long‐term stability. Overall, this project exhibits a reproducible method for large‐scale preparation of ultrathin bismuthene microsheets in a benign environment, demonstrating opportunities to realize devices based on bismuthene.     

Ultrafast Growth of High‐Quality Monolayer WSe2 on Au

The ultrafast growth of high‐quality uniform monolayer WSe₂ is reported with a growth rate of ≈26 µm s^?1 by chemical vapor deposition on reusable Au substrate, which is ≈2–3 orders of magnitude faster than those of most 2D transition metal dichalcogenides grown on nonmetal substrates. Such ultrafast growth allows for the fabrication of millimeter‐size single‐crystal WSe₂ domains in ≈30 s and large‐area continuous films in ≈60 s. Importantly, the ultrafast grown WSe₂ shows excellent crystal quality and extraordinary electrical performance comparable to those of the mechanically exfoliated samples, with a high mobility up to ≈143 cm² V^?1 s^?1 and ON/OFF ratio up to 9 × 10⁶ at room temperature. Density functional theory calculations reveal that the ultrafast growth of WSe₂ is due to the small energy barriers and exothermic characteristic for the diffusion and attachment of W and Se on the edges of WSe₂ on Au substrate.     

Ultrasonic‐Ball Milling: A Novel Strategy to Prepare Large‐Size Ultrathin 2D Materials

Large‐size ultrathin 2D materials, with extensive applications in optics, medicine, biology, and semiconductor fields, can be prepared through an existing common physical and chemical process. However, the current exfoliation technologies still need to be improved upon with urgency. Herein, a novel and simple “ultrasonic‐ball milling” strategy is reported to effectively obtain high quality and large size ultrathin 2D materials with complete lattice structure through the introduction of moderate sapphire (Al₂O₃) abrasives in a liquid phase system. Ultimately numerous high‐quality ultrathin h‐BN, graphene, MoS₂, WS₂, and BCN nanosheets are obtained with large sizes ranging from 1–20 µm, small thickness of ≈1–3 nm and a high yield of over 20%. Utilizing shear and friction force synergistically, this strategy provides a new method and alternative for preparing and optimizing large size ultrathin 2D materials.     

Synthesis of Large‐Area InSe Monolayers by Chemical Vapor Deposition

Recently, 2D materials of indium selenide (InSe) layers have attracted much attention from the scientific community due to their high mobility transport and fascinating physical properties. To date, reports on the synthesis of high‐quality and scalable InSe atomic films are limited. Here, a synthesis of InSe atomic layers by vapor phase selenization of In₂O₃ in a chemical vapor deposition (CVD) system, resulting in large‐area monolayer flakes or thin films, is reported. The atomic films are continuous and uniform over a large area of 1 × 1 cm², comprising of primarily InSe monolayers. Spectroscopic and microscopic measurements reveal the highly crystalline nature of the synthesized InSe monolayers. The ion‐gel‐gated field‐effect transistors based on CVD InSe monolayers exhibit n‐type channel behaviors, where the field effect electron mobility values can be up to ≈30 cm² V^?1 s^?1 along with an on/off current ratio, of >10⁴ at room temperature. In addition, the graphene can serve as a protection layer to prevent the oxidation between InSe and the ambient environment. Meanwhile, the synthesized InSe films can be transferred to arbitrary substrates, enabling the possibility of reassembly of various 2D materials into vertically stacked heterostructures, prompting research efforts to probe its characteristics and applications.     

Magnesium Storage Performance and Mechanism of 2D‐Ultrathin Nanosheet‐Assembled Spinel MgIn2S4 Cathode for High‐Temperature Mg Batteries

Magnesium batteries have the potential to be a next generation battery with large capability and high safety, owing to the high abundance, great volumetric energy density, and reversible dendrite‐free capability of Mg anodes. However, the lack of a stable high‐voltage electrolyte, and the sluggish Mg‐ion diffusion in lattices and through interfaces limit the practical uses of Mg batteries. Herein, a spinel MgIn₂S₄ microflower‐like material assembled by 2D‐ultrathin (≈5.0 nm) nanosheets is reported and first used as a cathode material for high‐temperature Mg batteries with an ionic liquid electrolyte. The nonflammable ionic liquid electrolyte ensure the safety under high temperatures. As prepared MgIn₂S₄ exhibits wide‐temperature‐range adaptability (50–150 °C), ultrahigh capacity (≈500 mAh g^?1 under 1.2 V vs Mg/Mg²⁺), fast Mg²⁺ diffusibility (≈2.0 × 10^?8 cm² s^?1), and excellent cyclability (without capacity decay after 450 cycles). These excellent electrochemical properties are due to the fast kinetics of magnesium by the 2D nanosheets spinel structure and safe high‐temperature operation environment. From ex situ X‐ray diffraction and transmission electron microscopy measurements, a conversion reaction of the Mg²⁺ storage mechanism is found. The excellent performance and superior security make it promising in high‐temperature batteries for practical applications.     

Aligned Heterointerface‐Induced 1T‐MoS2 Monolayer with Near‐Ideal Gibbs Free for Stable Hydrogen Evolution Reaction

1T‐phase molybdenum disulfide (1T‐MoS₂) exhibits superior hydrogen evolution reaction (HER) over 2H‐phase MoS₂ (2H‐MoS₂). However, its thermodynamic instability is the main drawback impeding its practical application. In this work, a stable 1T‐MoS₂ monolayer formed at edge‐aligned 2H‐MoS₂ and a reduced graphene oxide heterointerface (EA‐2H/1T/RGO) using a precursor‐in‐solvent synthesis strategy are reported. Theoretical prediction indicates that the edge‐aligned layer stacking can induce heterointerfacial charge transfer, which results in a phase transition of the interfacial monolayer from 2H to 1T that realizes thermodynamic stability based on the adhesion energy between MoS₂ and graphene. As an electrocatalyst for HER, EA‐2H/1T/RGO displays an onset potential of ?103 mV versus RHE, a Tafel slope of 46 mV dec^?1 and 10 h stability in acidic electrolyte. The unexpected activity of EA‐2H/1T/RGO beyond 1T‐MoS₂ is due to an inherent defect caused by the gliding of S atoms during the phase transition from 2H to 1T, leading the Gibbs free energy of hydrogen adsorption (ΔG_H*) to decrease from 0.13 to 0.07 eV, which is closest to the ideal value (0.06 eV) of 2H‐MoS₂. The presented work provides fundamental insights into the impressive electrochemical properties of HER and opens new avenues for phase transitions at 2D/2D hybrid interfaces.     

A Dopant Replacement‐Driven Molten Salt Method toward the Synthesis of Sub‐5‐nm‐Sized Ultrathin Nanowires

The high‐temperature molten‐salt method is an important inorganic synthetic route to a wide variety of morphological phenotypes. However, its utility is limited by the fact that it is typically incapable of producing ultrathin (<5 nm diameter) nanowires, which have a crucial role in novel nanotechnology applications. Herein, a rapid molten salt‐based synthesis of sub‐5‐nm‐sized nanowires of hexagonal tungsten oxide (h‐WO₃) that is critically dependent on a substantial proportion of molybdenum (Mo) dopant is described. This dopant‐driven morphological transition in tungsten oxide (WO₃) may be attributable to the collapse of layered structure, followed by nanocluster aggregation, coalescence, and recrystallization to form ultrathin nanowires. Interestingly, due to the structural properties of h‐WO₃, the thus‐formed ultrathin nanowires are demonstrated to be excellent photocatalysts for the production of ammonia (NH₃) from nitrogen (N₂) and water. The ultrathin nanowires exhibit a high photocatalytic NH₃‐production activity with a rate of 370 µmol g^?1 h^?1 and an apparent quantum efficiency of 0.84% at 420 nm, which is more than twice that obtained from the best‐performing Mo‐doped W₁₈O₄₉ nanowire catalysts. It is envisaged that the dopant replacement‐driven synthetic protocol will allow for rapid access to a series of ultrathin nanostructures with intriguing properties and increase potential applications.     

Colloidal Single‐Layer Photocatalysts for Methanol‐Storable Solar H2 Fuel

Molecular surfactants are widely used to control low‐dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single‐layer growth for 2D materials. A scalable stacking‐hinderable strategy to not only enable exclusive single‐layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single‐layer TMDs' photoredox activities is developed. The single‐layer growth mechanism is well explained by theoretical calculation. Three types of single‐layer TMDs, including MoS₂, WS₂, and ReS₂, are successfully synthesized and demonstrated in solar H₂ fuel production from hydrogen‐stored liquid carrier—methanol. Such H₂ fuel production from single‐layer MoS₂ nanosheets is CO_x‐free and reliably workable under room temperature and normal pressure with the generation rate reaching ≈617 µmole g^?1 h^?1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol‐storable solar H₂ fuel with facile chemical rebonding actualized by 2D single‐layer photocatalysts.     

Gap‐Mode Surface‐Plasmon‐Enhanced Photoluminescence and Photoresponse of MoS2

2D materials hold great potential for designing novel electronic and optoelectronic devices. However, 2D material can only absorb limited incident light. As a representative 2D semiconductor, monolayer MoS₂ can only absorb up to 10% of the incident light in the visible, which is not sufficient to achieve a high optical‐to‐electrical conversion efficiency. To overcome this shortcoming, a “gap‐mode” plasmon‐enhanced monolayer MoS₂ fluorescent emitter and photodetector is designed by squeezing the light‐field into Ag shell‐isolated nanoparticles–Au film gap, where the confined electromagnetic field can interact with monolayer MoS₂. With this gap‐mode plasmon‐enhanced configuration, a 110‐fold enhancement of photoluminescence intensity is achieved, exceeding values reached by other plasmon‐enhanced MoS₂ fluorescent emitters. In addition, a gap‐mode plasmon‐enhanced monolayer MoS₂ photodetector with an 880% enhancement in photocurrent and a responsivity of 287.5 A W^?1 is demonstrated, exceeding previously reported plasmon‐enhanced monolayer MoS₂ photodetectors.     

Lateral Graphene‐Contacted Vertically Stacked WS2/MoS2 Hybrid Photodetectors with Large Gain

A demonstration is presented of how significant improvements in all‐2D photodetectors can be achieved by exploiting the type‐II band alignment of vertically stacked WS₂/MoS₂ semiconducting heterobilayers and finite density of states of graphene electrodes. The photoresponsivity of WS₂/MoS₂ heterobilayer devices is increased by more than an order of magnitude compared to homobilayer devices and two orders of magnitude compared to monolayer devices of WS₂ and MoS₂, reaching 10³ A W^?1 under an illumination power density of 1.7 × 10² mW cm^?2. The massive improvement in performance is due to the strong Coulomb interaction between WS₂ and MoS₂ layers. The efficient charge transfer at the WS₂/MoS₂ heterointerface and long trapping time of photogenerated charges contribute to the observed large photoconductive gain of ≈3 × 10⁴. Laterally spaced graphene electrodes with vertically stacked 2D van der Waals heterostructures are employed for making high‐performing ultrathin photodetectors.     

Phase‐Controlled Synthesis of Monolayer W1−xRexS2 Alloy with Improved Photoresponse Performance

Tuning bandgap and phases in the ternary 2D transition metal dichalcogenides (TMDs) alloys has opened up unexpected opportunities to engineer optoelectronic properties and explore potential applications. In this work, a salt‐assisted chemical deposition vapor (CVD) growth strategy is reported for the creation of high‐quality monolayer W_1?xRe_xS₂ alloys to fulfill a readily phase control from 1H to DT by changing the ratio of Re and W precursors. The structures and chemical compositions of doping alloys are confirmed by combining atomic resolution scanning transmission electron microscopy‐annular dark field imaging with energy dispersive X‐ray spectroscopy (EDS) and X‐ray photoelectron spectroscopy, matching well with the calculated results. The field‐effect transistors (FETs) devices fabricated based on 1H‐W_0.9Re_0.1S₂ monolayer exhibit a n‐type semiconducting behavior with the mobility of 0.4 cm² V^?1 s^?1. More importantly, the FETs show high‐performance responsivity with a value of 17 µA W^?1 in air, which is superior to that of monolayer CVD‐grown WS₂. This work paves the way toward synthesizing monolayer ternary alloys with controlled phases for potential optoelectronic applications.     

A “Phase Separation” Molecular Design Strategy Towards Large‐Area 2D Molecular Crystals

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self‐assembly is considered an effective way to grow large‐area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self‐assembly and molecular structure. A “phase separation” molecular design strategy towards 2DMCs is proposed and layer‐by‐layer growth of millimeter‐sized monolayer or few‐layer 2DMCs is realized. High‐performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 10⁷), high responsivity (1.91 × 10⁴ A W^?1), and high detectivity (4.93 × 10¹⁵ Jones). This “phase separation” molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self‐assemble into large‐area 2DMCs for advanced organic (opto)electronics.     

Phase‐Tunable Synthesis of Ultrathin Layered Tetragonal CoSe and Nonlayered Hexagonal CoSe Nanoplates

Multiple structural phases in transition metal dichalcogenides have attracted considerable recent interest for their tunable chemical and electronic properties. Herein, a chemical vapor deposition route to ultrathin CoSe nanoplates with tunable structure phases is reported. By precisely tailoring the growth temperature, ultrathin 2D layered tetragonal CoSe nanoplates and nonlayered hexagonal CoSe nanoplates can be selectively prepared as square or hexagonal geometries, with thickness as thin as 2.3 and 3.7 nm, respectively. X‐ray diffraction, transmission electron microscopy, and selected area electron diffraction studies show that both types of nanoplates are high‐quality single crystals. Electrical transport studies reveal that both the tetragonal and hexagonal CoSe nanoplates show strong thickness‐tunable electrical properties and excellent breakdown current density. The 2D hexagonal CoSe nanoplates display metallic behavior with an excellent conductivity up to 6.6 × 10⁵ S m^?1 and an extraordinary breakdown current density up to 3.9 × 10⁷ A cm^?2, while the square tetragonal nanoplates show considerably lower conductivity up to 8.2 × 10⁴ S m^?1 with angle‐dependent magnetoresistance and weak antilocalization effect at lower field. This study offers a tunable material system for exploring multiphase 2D materials and their potential applications for electronic and magnetoelectronic devices.     

Wet/Sono‐Chemical Synthesis of Enzymatic Two‐Dimensional MnO2 Nanosheets for Synergistic Catalysis‐Enhanced Phototheranostics

2D nanomaterials have attracted broad interest in the field of biomedicine owing to their large surface area, high drug‐loading capacity, and excellent photothermal conversion. However, few studies report their “enzyme‐like” catalytic performance because it is difficult to prepare enzymatic nanosheets with small size and ultrathin thickness by current synthetic protocols. Herein, a novel one‐step wet‐chemical method is first proposed for protein‐directed synthesis of 2D MnO₂ nanosheets (M‐NSs), in which the size and thickness can be easily adjusted by the protein dosage. Then, a unique sono‐chemical approach is introduced for surface functionalization of the M‐NSs with high dispersity/stability as well as metal‐cation‐chelating capacity, which can not only chelate ⁶⁴Cu radionuclides for positron emission tomography (PET) imaging, but also capture the potentially released Mn²⁺ for enhanced biosafety. Interestingly, the resulting M‐NS exhibits excellent enzyme‐like activity to catalyze the oxidation of glucose, which represents an alternative paradigm of acute glucose oxidase for starving cancer cells and sensitizing them to thermal ablation. Featured with outstanding phototheranostic performance, the well‐designed M‐NS can achieve effective photoacoustic‐imaging‐guided synergistic starvation‐enhanced photothermal therapy. This study is expected to establish a new enzymatic phototheranostic paradigm based on small‐sized and ultrathin M‐NSs, which will broaden the application of 2D nanomaterials.     

Few‐Layer Silicene Nanosheets with Superior Lithium‐Storage Properties

Silicene, a 2D silicon allotrope with unique low‐buckled structure, has attracted increasing attention in recent years due to its many superior properties. So far, epitaxial growth is one of the very limited ways to obtain high‐quality silicene, which severely impedes the research and application of silicene. Therefore, large‐scale synthesis of silicene is a great challenge, yet urgently desired. Herein, the first scalable preparation of free‐standing high‐quality silicene nanosheets via liquid oxidation and exfoliation of CaSi₂ is reported. This new synthesis strategy successfully induces mild oxidation of the (Si²ⁿ)^2n? layers in CaSi₂ into neutral Si²ⁿ layers without damage of pristine silicene structure and promotes the exfoliation of stacked silicene layers. The obtained silicene sheets are dispersible and ultrathin ones with monolayer or few‐layer thickness and exhibit excellent crystallinity. As a unique 2D layered silicon allotrope, the silicene nanosheets are further explored as new anodes for lithium‐ion batteries and exhibit a nearly theoretical capacity of 721 mAh g^?1 at 0.1 A g^?1 and an extraordinary cycling stability with no capacity decay after 1800 cycles in contrast to previous most silicon anodes showing rapid capacity decay, thus holding great promise for energy storage and beyond.     

Protonation‐Assisted Exfoliation of N‐Containing 2D Conjugated Polymers

Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar‐to‐chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid‐phase protonation‐assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N‐containing conjugated polymers such as g‐C₃N₄, C₂N, and aza‐CMP. The exfoliation yields are only 2–15% in pure water whereas they can be substantially improved to 41–56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N‐containing conjugated polymer nanosheets for future solar energy conversion.     

Rapid and Low‐Temperature Salt‐Templated Production of 2D Metal Oxide/Oxychloride/Hydroxide

2D materials have played an important role in electronics, sensors, optics, electrocatalysis, and energy storage. Many methods for the preparation of 2D materials have been explored. It is crucial to develop a high‐yield, rapid, and low‐temperature method to synthesize 2D materials. A general, fast (5 min), and low‐temperature (≈100 °C) salt (CoCl₂·6H₂O)‐templated method is proposed to prepare series of 2D metal oxides/oxychlorides/hydroxides in large scale, such as MoO₃, SnO₂, SiO₂, BiOCl, Sb₄O₅Cl₂, Zn₂Co₃(OH)₁₀ 2H₂O, and ZnCo₂O₄. The as‐synthesized 2D materials possess an ultrathin feature (2–7 nm) and large aspect ratios. Additionally, these 2D metal oxides/oxychlorides/hydroxides exhibit good electrochemical properties in energy storage (lithium/sodium‐ion batteries) and electrocatalysis (hydrogen/oxygen evolution reaction).