Edge‐Epitaxial Growth of 2D NbS2‐WS2 Lateral Metal‐Semiconductor Heterostructures

2D metal‐semiconductor heterostructures based on transition metal dichalcogenides (TMDs) are considered as intriguing building blocks for various fields, such as contact engineering and high‐frequency devices. Although, a series of p–n junctions utilizing semiconducting TMDs have been constructed hitherto, the realization of such a scheme using 2D metallic analogs has not been reported. Here, the synthesis of uniform monolayer metallic NbS₂ on sapphire substrate with domain size reaching to a millimeter scale via a facile chemical vapor deposition (CVD) route is demonstrated. More importantly, the epitaxial growth of NbS₂‐WS₂ lateral metal‐semiconductor heterostructures via a “two‐step” CVD method is realized. Both the lateral and vertical NbS₂‐WS₂ heterostructures are achieved here. Transmission electron microscopy studies reveal a clear chemical modulation with distinct interfaces. Raman and photoluminescence maps confirm the precisely controlled spatial modulation of the as‐grown NbS₂‐WS₂ heterostructures. The existence of the NbS₂‐WS₂ heterostructures is further manifested by electrical transport measurements. This work broadens the horizon of the in situ synthesis of TMD‐based heterostructures and enlightens the possibility of applications based on 2D metal‐semiconductor heterostructures.     

Low‐Temperature Wafer‐Scale Deposition of Continuous 2D SnS2 Films

Semiconducting 2D materials, such as SnS₂, hold immense potential for many applications ranging from electronics to catalysis. However, deposition of few‐layer SnS₂ films has remained a great challenge. Herein, continuous wafer‐scale 2D SnS₂ films with accurately controlled thickness (2 to 10 monolayers) are realized by combining a new atomic layer deposition process with low‐temperature (250 °C) postdeposition annealing. Uniform coating of large‐area and 3D substrates is demonstrated owing to the unique self‐limiting growth mechanism of atomic layer deposition. Detailed characterization confirms the 1T‐type crystal structure and composition, smoothness, and continuity of the SnS₂ films. A two‐stage deposition process is also introduced to improve the texture of the films. Successful deposition of continuous, high‐quality SnS₂ films at low temperatures constitutes a crucial step toward various applications of 2D semiconductors.     

Covalent‐Organic‐Framework‐Based Li–CO2 Batteries

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials constructed from designer molecular building blocks that are linked and extended periodically via covalent bonds. Their high stability, open channels, and ease of functionalization suggest that they can function as a useful cathode material in reversible lithium batteries. Here, a COF constructed from hydrazone/hydrazide‐containing molecular units, which shows good CO₂ sequestration properties, is reported. The COF is hybridized to Ru‐nanoparticle‐coated carbon nanotubes, and the composite is found to function as highly efficient cathode in a Li–CO₂ battery. The robust 1D channels in the COF serve as CO₂^– and lithium‐ion‐diffusion channels and improve the kinetics of electrochemical reactions. The COF‐based Li–CO₂ battery exhibits an ultrahigh capacity of 27 348 mAh g^?1 at a current density of 200 mA g^?1, and a low cut‐off overpotential of 1.24 V within a limiting capacity of 1000 mAh g^?1. The rate performance of the battery is improved considerably with the use of the COF at the cathode, where the battery shows a slow decay of discharge voltage from a current density of 0.1 to 4 A g^?1. The COF‐based battery runs for 200 cycles when discharged/charged at a high current density of 1 A g^?1.     

In‐Plane 2H‐1T′ MoTe2 Homojunctions Synthesized by Flux‐Controlled Phase Engineering

The fabrication of in‐plane 2H‐1T′ MoTe₂ homojunctions by the flux‐controlled, phase‐engineering of few‐layer MoTe₂ from Mo nanoislands is reported. The phase of few‐layer MoTe₂ is controlled by simply changing Te atomic flux controlled by the temperature of the reaction vessel. Few‐layer 2H MoTe₂ is formed with high Te flux, while few‐layer 1T′ MoTe₂ is obtained with low Te flux. With medium flux, few‐layer in‐plane 2H‐1T′ MoTe₂ homojunctions are synthesized. As‐synthesized MoTe₂ is characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy. Kelvin probe force microscopy and Raman mapping confirm that in‐plane 2H‐1T′ MoTe₂ homojunctions have abrupt interfaces between 2H and 1T′ MoTe₂ domains, possessing a potential difference of about 100 mV. It is further shown that this method can be extended to create patterned metal–semiconductor junctions in MoTe₂ in a two‐step lithographic synthesis. The flux‐controlled phase engineering method could be utilized for the large‐scale controlled fabrication of 2D metal–semiconductor junctions for next‐generation electronic and optoelectronic devices.     

Tunable Polarity Behavior and Self‐Driven Photoswitching in p‐WSe2/n‐WS2 Heterojunctions

Van der Waals (vdW) p–n heterojunctions consisting of various 2D layer compounds are fascinating new artificial materials that can possess novel physics and functionalities enabling the next‐generation of electronics and optoelectronics devices. Here, it is reported that the WSe₂/WS₂ p–n heterojunctions perform novel electrical transport properties such as distinct rectifying, ambipolar, and hysteresis characteristics. Intriguingly, the novel tunable polarity transition along a route of n‐“anti‐bipolar”–p‐ambipolar is observed in the WSe₂/WS₂ heterojunctions owing to the successive work of conducting channels of junctions, p‐WSe₂ and n‐WS₂ on the electrical transport of the whole systems. The type‐II band alignment obtained from first principle calculations and built‐in potential in this vdW heterojunction can also facilitate the efficient electron–hole separation, thus enabling the significant photovoltaic effect and a much enhanced self‐driven photoswitching response in this system.     

Liquid‐Alloy‐Assisted Growth of 2D Ternary Ga2In4S9 toward High‐Performance UV Photodetection

2D ternary systems provide another degree of freedom of tuning physical properties through stoichiometry variation. However, the controllable growth of 2D ternary materials remains a huge challenge that hinders their practical applications. Here, for the first time, by using a gallium/indium liquid alloy as the precursor, the synthesis of high‐quality 2D ternary Ga₂In₄S₉ flakes of only a few atomic layers thick (≈2.4 nm for the thinnest samples) through chemical vapor deposition is realized. Their UV‐light‐sensing applications are explored systematically. Photodetectors based on the Ga₂In₄S₉ flakes display outstanding UV detection ability (R _λ = 111.9 A W^?1, external quantum efficiency = 3.85 × 10⁴%, and D* = 2.25 × 10¹¹ Jones@360 nm) with a fast response speed (τ_ring ≈ 40 ms and τ_decay ≈ 50 ms). In addition, Ga₂In₄S₉‐based phototransistors exhibit a responsivity of ≈10⁴ A W^?1@360 nm above the critical back‐gate bias of ≈0 V. The use of the liquid alloy for synthesizing ultrathin 2D Ga₂In₄S₉ nanostructures may offer great opportunities for designing novel 2D optoelectronic materials to achieve optimal device performance.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

Active Targeting Using HER‐2‐Affibody‐Conjugated Nanoparticles Enabled Sensitive and Specific Imaging of Orthotopic HER‐2 Positive Ovarian Tumors

Despite advances in cancer diagnosis and treatment, ovarian cancer remains one of the most fatal cancer types. The development of targeted nanoparticle imaging probes and therapeutics offers promising approaches for early detection and effective treatment of ovarian cancer. In this study, HER‐2 targeted magnetic iron oxide nanoparticles (IONPs) are developed by conjugating a high affinity and small size HER‐2 affibody that is labeled with a unique near infrared dye (NIR‐830) to the nanoparticles. Using a clinically relevant orthotopic human ovarian tumor xenograft model, it is shown that HER‐2 targeted IONPs are selectively delivered into both primary and disseminated ovarian tumors, enabling non‐invasive optical and MR imaging of the tumors as small as 1 mm in the peritoneal cavity. It is determined that HER‐2 targeted delivery of the IONPs is essential for specific and sensitive imaging of the HER‐2 positive tumor since we are unable to detect the imaging signal in the tumors following systemic delivery of non‐targeted IONPs into the mice bearing HER‐2 positive SKOV3 tumors. Furthermore, imaging signals and the IONPs are not detected in HER‐2 low expressing OVCAR3 tumors after systemic delivery of HER‐2 targeted‐IONPs. Since HER‐2 is expressed in a high percentage of ovarian cancers, the HER‐2 targeted dual imaging modality IONPs have potential for the development of novel targeted imaging and therapeutic nanoparticles for ovarian cancer detection, targeted drug delivery, and image‐guided therapy and surgery.     

Synthesis of Few‐Layer MoS2 Nanosheet‐Coated TiO2 Nanobelt Heterostructures for Enhanced Photocatalytic Activities

MoS₂ nanosheet‐coated TiO₂ nanobelt heterostructures—referred to as TiO₂@MoS₂—with a 3D hierarchical configuration are prepared via a hydrothermal reaction. The TiO₂ nanobelts used as a synthetic template inhibit the growth of MoS₂ crystals along the c‐axis, resulting in a few‐layer MoS₂ nanosheet coating on the TiO₂ nanobelts. The as‐prepared TiO₂@MoS₂ heterostructure shows a high photocatalytic hydrogen production even without the Pt co‐catalyst. Importantly, the TiO₂@MoS₂ heterostructure with 50 wt% of MoS₂ exhibits the highest hydrogen production rate of 1.6 mmol h^?1g^?1. Moreover, such a heterostructure possesses a strong adsorption ability towards organic dyes and shows high performance in photocatalytic degradation of the dye molecules.     

Large‐Area Atomic Layers of the Charge‐Density‐Wave Conductor TiSe2

Layered transition metal (Ti, Ta, Nb, etc.) dichalcogenides are important prototypes for the study of the collective charge density wave (CDW). Reducing the system dimensionality is expected to lead to novel properties, as exemplified by the discovery of enhanced CDW order in ultrathin TiSe₂. However, the syntheses of monolayer and large‐area 2D CDW conductors can currently only be achieved by molecular beam epitaxy under ultrahigh vacuum. This study reports the growth of monolayer crystals and up to 5 × 10⁵ µm² large films of the typical 2D CDW conductor—TiSe₂—by ambient‐pressure chemical vapor deposition. Atomic resolution scanning transmission electron microscopy indicates the as‐grown samples are highly crystalline 1T‐phase TiSe₂. Variable‐temperature Raman spectroscopy shows a CDW phase transition temperature of 212.5 K in few layer TiSe₂, indicative of high crystal quality. This work not only allows the exploration of many‐body state of TiSe₂ in 2D limit but also offers the possibility of utilizing large‐area TiSe₂ in ultrathin electronic devices.     

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.