Highly Anisotropic Sb2Se3 Nanosheets: Gentle Exfoliation from the Bulk Precursors Possessing 1D Crystal Structure

2D materials, particularly those bearing in‐plane anisotropic optical and electrical properties such as black phosphorus and ReS₂, have spurred great research interest very recently as promising building blocks for future electronics. However, current progress is limited to layered compounds that feature atomic arrangement asymmetry within the covalently bonded planes. Herein, a series of highly anisotropic nanosheets (Sb₂Se₃, Sb₂S₃, Bi₂S₃, and Sb₂(S, Se)₃), which are composed of 1D covalently linked ribbons stacked together via van der Waals force, is introduced as a new member to the anisotropic 2D material family. These unique anisotropic nanosheets are successfully fabricated from their polymer‐like bulk counterparts through a gentle water freezing‐thawing approach. Angle‐resolved polarized Raman spectroscopy characterization confirms the strong in‐plane asymmetry of Sb₂Se₃ nanosheets, and photodetection study reveals their high responsivity and anisotropic in‐plane transport. This work can enlighten the synthesis and application of new anisotropic 2D nanosheets that can be potentially applied for future electronic and optoelectronic devices.     

Chemical Patterning of High‐Mobility Semiconducting 2D Bi2O2Se Crystals for Integrated Optoelectronic Devices

Patterning of high‐mobility 2D semiconducting materials with unique layered structures and superb electronic properties offers great potential for batch fabrication and integration of next‐generation electronic and optoelectronic devices. Here, a facile approach is used to achieve accurate patterning of 2D high‐mobility semiconducting Bi₂O₂Se crystals using dilute H₂O₂ and protonic mixture acid as efficient etchants. The 2D Bi₂O₂Se crystal after chemical etching maintains a high Hall mobility of over 200 cm² V^?1 s^?1 at room temperature. Centimeter‐scale well‐ordered arrays of 2D Bi₂O₂Se with tailorable configurations are readily obtained. Furthermore, integrated photodetectors based on 2D Bi₂O₂Se arrays are fabricated, exhibiting excellent air stability and high photoresponsivity of ≈2000 A W^?1 at 532 nm. These results are one step towards the practical application of ultrathin 2D integrated digital and optoelectronic circuits.     

Interface‐Driven Partial Dislocation Formation in 2D Heterostructures

Van der Waals (vdW) epitaxy allows the fabrication of various heterostructures with dramatically released lattice matching conditions. This study demonstrates interface‐driven stacking boundaries in WS₂ using epitaxially grown tungsten disulfide (WS₂) on wrinkled graphene. Graphene wrinkles function as highly reactive nucleation sites on WS₂ epilayers; however, they impede lateral growth and induce additional stress in the epilayer due to anisotropic friction. Moreover, partial dislocation‐driven in‐plane strain facilitates out‐of‐plane buckling with a height of 1 nm to release in‐plane strain. Remarkably, in‐plane strain relaxation at partial dislocations restores the bandgap to that of monolayer WS₂ due to reduced interlayer interaction. These findings clarify significant substrate morphology effects even in vdW epitaxy and are potentially useful for various applications involving modifying optical and electronic properties by manipulating extended 1D defects via substrate morphology control.     

3R MoS2 with Broken Inversion Symmetry: A Promising Ultrathin Nonlinear Optical Device

Nonlinear 2D layered crystals provide ideal platforms for applications and fundamental studies in ultrathin nonlinear optical (NLO) devices. However, the NLO frequency conversion efficiency constrained by lattice symmetry is still limited by layer numbers of 2D crystals. In this work, 3R MoS₂ with broken inversion symmetry structure are grown and proved to be excellent NLO 2D crystals from monolayer (0.65 nm) toward bulk‐like (300 nm) dimension. Thickness and wavelength‐dependent second harmonic generation spectra offer the selection rules of appropriate working conditions. A model comprising of bulk nonlinear contribution and interface interaction is proposed to interpret the observed nonlinear behavior. Polarization enhancement with two petals along staggered stacking direction appears in 3R MoS₂ is first observed and the robust polarization of 3R MoS₂ crystal is caused by the retained broken inversion symmetry. The results provide a new arena for realizing ultrathin NLO devices for 2D layered materials.     

Flexible and High‐Performance All‐2D Photodetector for Wearable Devices

Emerging novel applications at the forefront of innovation horizon raise new requirements including good flexibility and unprecedented properties for the photoelectronic industry. On account of diversity in transport and photoelectric properties, 2D layered materials have proven as competent building blocks toward next‐generation photodetectors. Herein, an all‐2D Bi₂Te₃‐SnS‐Bi₂Te₃ photodetector is fabricated with pulsed‐laser deposition. It is sensitive to broadband wavelength from ultraviolet (370 nm) to near‐infrared (808 nm). In addition, it exhibits great durability to bend, with intact photoresponse after 100 bend cycles. Upon 370 nm illumination, it achieves a high responsivity of 115 A W^?1, a large external quantum efficiency of 3.9 × 10⁴%, and a superior detectivity of 4.1 × 10¹¹ Jones. They are among the best figures‐of‐merit of state‐of‐the‐art 2D photodetectors. The synergistic effect of SnS's strong light–matter interaction, efficient carrier separation of Bi₂Te₃–SnS interface, expedite carrier injection across Bi₂Te₃–SnS interface, and excellent carrier collection of Bi₂Te₃ topological insulator electrodes accounts for the superior photodetection properties. In summary, this work depicts a facile all‐in‐one fabrication strategy toward a Bi₂Te₃‐SnS‐Bi₂Te₃ photodetector. More importantly, it reveals a novel all‐2D concept for construction of flexible, broadband, and high‐performance photoelectronic devices by integrating 2D layered metallic electrodes and 2D layered semiconducting channels.     

Epitaxial Growth of Ternary Topological Insulator Bi2Te2Se 2D Crystals on Mica

Nanostructures of ternary topological insulator (TI) Bi₂Te₂Se are, in principle, advantageous to the manifestation of topologically nontrivial surface states, due to significantly enhanced surface‐to‐volume ratio compared with its bulk crystals counterparts. Herein, the synthesis of 2D Bi₂Te₂Se crystals on mica via the van der Waals epitaxy method is explored and systematically the growth behaviors during the synthesis process are investigated. Accordingly, 2D Bi₂Te₂Se crystals with domain size up to 50 µm large and thickness down to 2 nm are obtained. A pronounced weak antilocalization effect is clearly observed in the 2D Bi₂Te₂Se crystals at 2 K. The method for epitaxial growth of 2D ternary Bi₂Te₂Se crystals may inspire materials engineering toward enhanced manifestation of the subtle surface states of TIs and thereby facilitate their potential applications in next‐generation spintronics.     

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.     

Phase Engineering of 2D Tin Sulfides

Tin sulfides can exist in a variety of phases and polytypes due to the different oxidation states of Sn. A subset of these phases and polytypes take the form of layered 2D structures that give rise to a wide host of electronic and optical properties. Hence, achieving control over the phase, polytype, and thickness of tin sulfides is necessary to utilize this wide range of properties exhibited by the compound. This study reports on phase‐selective growth of both hexagonal tin (IV) sulfide SnS₂ and orthorhombic tin (II) sulfide SnS crystals with diameters of over tens of microns on SiO₂ substrates through atmospheric pressure vapor‐phase method in a conventional horizontal quartz tube furnace with SnO₂ and S powders as the source materials. Detailed characterization of each phase of tin sulfide crystals is performed using various microscopy and spectroscopy methods, and the results are corroborated by ab initio density functional theory calculations.     

Air-Stable Low-Symmetry Narrow-Bandgap 2D Sulfide Niobium for Polarization Photodetection

Low-symmetry 2D materials with unique anisotropic optical and optoelectronic characteristics have attracted a lot of interest in fundamental research and manufacturing of novel optoelectronic devices. Exploring new and low-symmetry narrow-bandgap 2D materials will be rewarding for the development of nanoelectronics and nano-optoelectronics. Herein, sulfide niobium (NbS₃), a novel transition metal trichalcogenide semiconductor with low-symmetry structure, is introduced into a narrowband 2D material with strong anisotropic physical properties both experimentally and theoretically. The indirect bandgap of NbS₃ with highly anisotropic band structures slowly decreases from 0.42 eV (monolayer) to 0.26 eV (bulk). Moreover, NbS₃ Schottky photodetectors have excellent photoelectric performance, which enables fast photoresponse (11.6 µs), low specific noise current (4.6 × 10⁻²⁵ A² Hz⁻¹), photoelectrical dichroic ratio (1.84) and high-quality reflective polarization imaging (637 nm and 830 nm). A room-temperature specific detectivity exceeding 10⁷ Jones can be obtained at the wavelength of 3 µm. These excellent unique characteristics will make low-symmetry narrow-bandgap 2D materials become highly competitive candidates for future anisotropic optical investigations and mid-infrared optoelectronic applications.     

3D Anisotropic Thermal Conductivity of Exfoliated Rhenium Disulfide

ReS₂ represents a different class of 2D materials, which is characterized by low symmetry having 1D metallic chains within the planes and extremely weak interlayer bonding. Here, the thermal conductivity of single‐crystalline ReS₂ in a distorted 1T phase is determined at room temperature for the in‐plane directions parallel and perpendicular to the Re‐chains, and the through‐plane direction using time‐domain thermoreflectance. ReS₂ is prepared in the form of flakes having thicknesses of 60–450 nm by micromechanical exfoliation, and their crystalline orientations are identified by polarized Raman spectroscopy. The in‐plane thermal conductivity is higher along the Re‐chains, (70 ± 18) W m^?1 K^?1, as compared to transverse to the chains, (50 ± 13) W m^?1 K^?1. As expected from the weak interlayer bonding, the through‐plane thermal conductivity is the lowest observed to date for 2D materials, (0.55 ± 0.07) W m^?1 K^?1, resulting in a remarkably high anisotropy of (130 ± 40) and (90 ± 30) for the two in‐plane directions. The thermal conductivity and interface thermal conductance of ReS₂ are discussed relative to the other 2D materials.     

Birefringence‐Directed Raman Selection Rules in 2D Black Phosphorus Crystals

The incident and scattered light engaged in the Raman scattering process of low symmetry crystals always suffer from the birefringence‐induced depolarization. Therefore, for anisotropic crystals, the classical Raman selection rules should be corrected by taking the birefringence effect into consideration. The appearance of the 2D anisotropic materials provides an excellent platform to explore the birefringence‐directed Raman selection rules, due to its controllable thickness at the nanoscale that greatly simplifies the situation comparing with bulk materials. Herein, a theoretical and experimental investigation on the birefringence‐directed Raman selection rules in the anisotropic black phosphorus (BP) crystals is presented. The abnormal angle‐dependent polarized Raman scattering of the A_g modes in thin BP crystal, which deviates from the normal Raman selection rules, is successfully interpreted by the theoretical model based on birefringence. It is further confirmed by the examination of different Raman modes using different laser lines and BP samples of different thicknesses.     

High‐Throughput Continuous Production of Shear‐Exfoliated 2D Layered Materials using Compressible Flows

2D nanomaterials are finding numerous applications in next‐generation electronics, consumer goods, energy generation and storage, and healthcare. The rapid rise of utility and applications for 2D nanomaterials necessitates developing means for their mass production. This study details a new compressible flow exfoliation method for producing 2D nanomaterials using a multiphase flow of 2D layered materials suspended in a high‐pressure gas undergoing expansion. The expanded gas–solid mixture is sprayed in a suitable solvent, where a significant portion (up to 10% yield) of the initial hexagonal boron nitride material is found to be exfoliated with a mean thickness of 4.2 nm. The exfoliation is attributed to the high shear rates ( > 10⁵ s^?1) generated by supersonic flow of compressible gases inside narrow orifices and converging‐diverging channels. This method has significant advantages over current 2D material exfoliation methods, such as chemical intercalation and exfoliation, as well as liquid phase shear exfoliation, with the most obvious benefit being the fast, continuous nature of the process. Other advantages include environmentally friendly processing, reduced occurrence of defects, and the versatility to be applied to any 2D layered material using any gaseous medium. Scaling this process to industrial production has a strong possibility of reducing the cost of creating 2D nanomaterials.     

Colloids of Holey Gd2O3 Nanosheets Converted from Exfoliated Gadolinium Hydroxide Layers

This paper proposes a confined solid‐state conversion approach using layered metal‐hydroxides for the production of a colloidal suspension of porous 2D crystalline metal oxide layers with superior electrochemical H₂O₂ sensing performance. This study investigates the conversion chemistry of delaminated layers of gadolinium hydroxide (LGdH), [Gd₂(OH)₅]⁺, encapsulated in a silica nanoshell that provides an antistacking and antisintering environment during the phase‐transition at high temperature. Thermal treatment of the LGdH layers within the protected environment results in a dimensionally confined phase‐transition into crystalline Gd₂O₃ nanosheets with an isomorphic 2D structure. Furthermore, annealing at higher temperatures leads to the evolution of in‐plane mesoporous structure on the Gd₂O₃ nanosheet. Based on insight acquired from in‐depth investigation, the evolution of in‐plane porosity proceeds through the in‐plane dominant silicate‐formation reaction at the interface with the surrounding silica shell. Their 2D‐anisotropic and mesoporous morphological features are preserved, producing a colloidal suspension of holey nanosheets that can be used to fabricate a thin and porous film through wet‐coating deposition. This study also demonstrates the superior electrochemical H₂O₂ sensing ability of the resultant porous Gd₂O₃ film, which represents a ≈1000‐ and 10‐fold enhancement of the detection limit and sensitivity, respectively, in comparison to previously reported Gd₂O₃ films.     

From Amorphous Macroporous Film to 3D Crystalline Nanorod Architecture: A New Approach to Obtain High‐Performance V2O5 Electrochromism

A 3D crystalline V₂O₅ nanorod architecture on indium tin oxide substrates is prepared by simple annealing treatment of a colloidal crystal‐assisted electrodeposited amorphous three‐dimensionally ordered macroporous film at a low temperature of 350 °C. The crystalline nanorods exhibit a low length/diameter ratio with the typical width range of 80–180 nm, length range of 190–500 nm, and thickness of 30–50 nm. Colloidal sphere‐assisted heterogeneous nucleation during electrodeposition and the anisotropic bonding of the V₂O₅‐layered structure are two important factors for the morphological changes. Because of the large surface area, short lithium ion diffusion distance, and good electrolyte penetration, the 3D crystalline V₂O₅ nanorod architecture exhibits a highly reversible Li‐ion insertion/extraction process (columbic efficiency up to 96.9%) with a five‐color‐change electrochromic performance, good transmittance modulation, and acceptable response times (8.8 s for coloration and 9.3 s for bleaching), making it a promising film electrode for electrochromic devices.     

Enhancing Interconnect Reliability and Performance by Converting Tantalum to 2D Layered Tantalum Sulfide at Low Temperature

The interconnect half‐pitch size will reach ≈20 nm in the coming sub‐5 nm technology node. Meanwhile, the TaN/Ta (barrier/liner) bilayer stack has to be >4 nm to ensure acceptable liner and diffusion barrier properties. Since TaN/Ta occupy a significant portion of the interconnect cross‐section and they are much more resistive than Cu, the effective conductance of an ultrascaled interconnect will be compromised by the thick bilayer. Therefore, 2D layered materials have been explored as diffusion barrier alternatives. However, many of the proposed 2D barriers are prepared at too high temperatures to be compatible with the back‐end‐of‐line (BEOL) technology. In addition, as important as the diffusion barrier properties, the liner properties of 2D materials must be evaluated, which has not yet been pursued. Here, a 2D layered tantalum sulfide (TaS_x ) with ≈1.5 nm thickness is developed to replace the conventional TaN/Ta bilayer. The TaS_x ultrathin film is industry‐friendly, BEOL‐compatible, and can be directly prepared on dielectrics. The results show superior barrier/liner properties of TaS_x compared to the TaN/Ta bilayer. This single‐stack material, serving as both a liner and a barrier, will enable continued scaling of interconnects beyond 5 nm node.     

Molecular Beam Epitaxy and Electronic Structure of Atomically Thin Oxyselenide Films

Atomically thin oxychalcogenides have been attracting intensive attention for their fascinating fundamental properties and application prospects. Bi₂O₂Se, a representative of layered oxychalcogenides, has emerged as an air‐stable high‐mobility 2D semiconductor that holds great promise for next‐generation electronics. The preparation and device fabrication of high‐quality Bi₂O₂Se crystals down to a few atomic layers remains a great challenge at present. Here, molecular beam epitaxy (MBE) of atomically thin Bi₂O₂Se films down to monolayer on SrTiO₃ (001) substrate is achieved by co‐evaporating Bi and Se precursors in oxygen atmosphere. The interfacial atomic arrangements of MBE‐grown Bi₂O₂Se/SrTiO₃ are unambiguously revealed, showing an atomically sharp interface and atom‐to‐atom alignment. Importantly, the electronic band structures of one‐unit‐cell (1‐UC) thick Bi₂O₂Se films are observed by angle‐resolved photoemission spectroscopy (ARPES), showing low effective mass of ≈0.15 m₀ and bandgap of ≈0.8 eV. These results may be constructive to the synthesis of other 2D oxychalcogenides and investigation of novel physical properties.     

Environmentally‐Friendly Exfoliate and Active Site Self‐Assembly: Thin 2D/2D Heterostructure Amorphous Nickel–Iron Alloy on 2D Materials for Efficient Oxygen Evolution Reaction

A class of 2D layered materials exhibits substantial potential for high‐performance electrocatalysts due to high specific surface area, tunable electronic properties, and open 2D channels for fast ion transport. However, liquid‐phase exfoliation always utilizes organic solvents that are harmful to the environment, and the active sites are limited to edge sites. Here, an environmentally friendly exfoliator in aqueous solution is presented without utilizing any toxic or hazardous substance and active site self‐assembly on the inert base of 2D materials. Benefiting from thin 2D/2D heterostructure and strong interfacial coupling, the resultant highly disordered amorphous NiFe/2D materials (Ti3C2 MXene, graphene and MoS₂) thin nanosheets exhibit extraordinary electrocatalytic performance toward oxygen evolution reaction (OER) in alkaline media. DFT results further verify the experimental results. The study emphasizes a viable idea to probe efficient electrocatalysts by means of the synergistic effect of environmentally friendly exfoliator in aqueous solution and active site self‐assembly on the inert base of 2D materials which forms the unique thin 2D/2D heterostructure in‐suit. This new type of heterostructure opens up a novel avenue for the rational design of highly efficient 2D materials for electrocatalysis.     

Large Intercalation Pseudocapacitance in 2D VO2 (B): Breaking through the Kinetic Barrier

VO₂ (B) features two lithiation/delithiation processes, one of which is kinetically facile and has been commonly observed at 2.5 V versus Li/Li⁺ in various VO₂ (B) structures. In contrast, the other process, which occurs at 2.1 V versus Li/Li⁺, has only been observed at elevated temperatures due to large interaction energy barrier and extremely sluggish kinetics. Here, it is demonstrated that a rational design of atomically thin, 2D nanostructures of VO₂ (B) greatly lowers the interaction energy and Li⁺‐diffusion barrier. Consequently, the kinetically sluggish step is successfully enabled to proceed at room temperature for the first time ever. The atomically thin 2D VO₂ (B) exhibits fast charge storage kinetics and enables fully reversible uptake and removal of Li ions from VO₂ (B) lattice without a phase change, resulting in exceptionally high performance. This work presents an effective strategy to speed up intrinsically sluggish processes in non‐van der Waals layered materials.     

Ultrathin Single‐Crystalline CdTe Nanosheets Realized via Van der Waals Epitaxy

Due to the novel physical properties, high flexibility, and strong compatibility with Si‐based electronic techniques, 2D nonlayered structures have become one of the hottest topics. However, the realization of 2D structures from nonlayered crystals is still a critical challenge, which requires breaking the bulk crystal symmetry and guaranteeing the highly anisotropic crystal growth. CdTe owns a typical wurtzite crystal structure, which hinders the 2D anisotropic growth of hexagonal‐symmetry CdTe. Here, for the first time, the 2D anisotropic growth of ultrathin nonlayered CdTe as thin as 4.8 nm via an effective van der Waals epitaxy method is demonstrated. The anisotropic ratio exceeds 10³. Highly crystalline nanosheets with uniform thickness and large lateral dimensions are obtained. The in situ fabricated ultrathin 2D CdTe photodetector shows ultralow dark current (≈100 fA), as well as high detectivity, stable photoswitching, and fast photoresponse speed (τ_rising = 18.4 ms, τ_decay = 14.7 ms). Besides, benefitting from its 2D planar geometry, CdTe nanosheet exhibits high compatibility with flexible substrates and traditional microfabrication techniques, indicating its significant potential in the applications of flexible electronic and optoelectronic devices.     

Salt-Assisted Low-Temperature Growth of 2D Bi2O2Se with Controlled Thickness for Electronics

Bi₂O₂Se is the most promising 2D material due to its semiconducting feature and high mobility, making it propitious channel material for high-performance electronics that demands highly crystalline Bi₂O₂Se at low-growth temperature. Here, a low-temperature salt-assisted chemical vapor deposition approach for growing single-domain Bi₂O₂Se on a millimeter scale with thicknesses of multilayer to monolayer is presented. Because of the advantage of thickness-dependent growth, systematical scrutiny of layer-dependent Raman spectroscopy of Bi₂O₂Se from monolayer to bulk is investigated, revealing a redshift of the A_1g mode at 162.4 cm⁻¹. Moreover, the long-term environmental stability of ≈2.4 nm thick Bi₂O₂Se is confirmed after exposing the sample for 1.5 years to air. The backgated field effect transistor (FET) based on a few-layered Bi₂O₂Se flake represents decent carrier mobility (≈287 cm² V⁻¹s⁻¹) and an ON/OFF ratio of up to 10⁷. This report indicates a technique to grow large-domain thickness controlled Bi₂O₂Se single crystals for electronics.