Black phosphorus (BP) is a rapidly up and coming star in two‐dimensional (2D) materials. The unique characteristic of BP is its in‐plane anisotropy. This characteristic of BP ignites a new type of 2D materials that have low‐symmetry structures and in‐plane anisotropic properties. On this basis, they offer richer and more unique low‐dimensional physics compared to isotropic 2D materials, thus providing a fertile ground for novel applications including electronics, optoelectronics, molecular detection, thermoelectric, piezoelectric, and ferroelectric with respect to in‐plane anisotropy. This article reviews the recent advance in characterization and applications of in‐plane anisotropic 2D materials.

Two-dimensional molecular crystals, consisting of zero-dimensional molecules, are very appealing due to their novel physical properties. However, they are mostly limited to organic molecules. The synthesis of inorganic version of two-dimensional molecular crystals is still a challenge due to the difficulties in controlling the crystal phase and growth plane. Here, we design a passivator-assisted vapor deposition method for the growth of two-dimensional Sb2O3 inorganic molecular crystals as thin as monolayer. The passivator can prevent the heterophase nucleation and suppress the growth of low-energy planes, and enable the molecule-by-molecule lateral growth along high-energy planes. Using Raman spectroscopy and in situ transmission electron microscopy, we show that the insulating α-phase of Sb2O3 flakes can be transformed into semiconducting β-phase under heat and electron-beam irradiation. Our findings can be extended to the controlled growth of other two-dimensional inorganic molecular crystals and open up opportunities for potential molecular electronic devices.

Due to the intriguing anisotropic optical and electrical properties, low‐symmetry 2D materials are attracting a lot of interest both for fundamental studies and fabricating novel electronic and optoelectronic devices. Identifying new promising low‐symmetry 2D materials will be rewarding toward the evolution of nanoelectronics and nano‐optoelectronics. In this work, germanium diarsenide (GeAs2), a group IV–V semiconductor with novel low‐symmetry puckered structure, is introduced as a favorable highly anisotropic 2D material into the rapidly growing 2D family. The structural, vibrational, electrical, and optical in‐plane anisotropy of GeAs2 is systematically investigated both theoretically and experimentally, combined with thickness‐dependent studies. Polarization‐sensitive photodetectors based on few‐layer GeAs2 exhibit highly anisotropic photodetection behavior with lineally dichroic ratio up to ≈2. This work on GeAs2 will excite interests in the less exploited regime of group IV–V compounds.

Van der Waals (vdW) dielectrics such as hBN are widely used to preserve the intrinsic properties of twodimensional (2D) semiconductors and support the fabrication of high-performance 2D devices. This is fundamentally attributed to their dangling-bond-free surface, carrying far lower density of charged scattering sources and trap states with respect to the conventional dielectrics (SiO 2 etc.). However, their wafer-scale fabrication and compatible integration with 2D semiconductors remain cumbersome, giving rise to the di culties in scalable fabrication of high-performance 2D devices. Here we report a high-κ vdW dielectric (ε r =11.5) composed of inorganic molecular crystal (IMC) Sb 2 O 3 , allowing for large-scale fabrication and facile integration via standard thermal evaporation process thanks to its particular crystal structure. Similarly, our vdW dielectric also supports remarkably improved 2D devices with respect to the typical conventional dielectric SiO 2 . The monolayer MoS 2 eld effect transistors (FET) supported by our vdW dielectric exhibits high on/off ratio (10 8 ), greatly enhanced electron mobility (from 20 to 80 cm 2 /Vs) and reduced transfer-curve hysteresis over an order of magnitude. Our results may open a new avenue towards compatible fabrication of vdW dielectrics using IMCs and lead to the scalable fabrication of high-performance 2D devices.

Infrared (IR) photodetectors are finding diverse applications in imaging, information communication, military, etc. 2D metal chalcogenides (2DMCs) have attracted increasing interest in view of their unique structures and extraordinary physical properties. They have demonstrated outstanding IR detection performance including high responsivity and detectivity, high on/off ratio, fast response rate, stable room temperature operability, and good mechanical flexibility, which has opened up a new prospect in next‐generation IR photodetectors. This Review presents a comprehensive summary of recent progress in advanced IR photodetectors based on 2DMCs. The rationale of the photodetectors containing photocurrent generation mechanisms and performance parameters are briefly introduced. The device performances of 2DMCs‐based IR photodetectors are also systematically summarized, and some representative achievements are highlighted as well. Finally, conclusions and outlooks are delivered as a guideline for this thriving field.

We synthesized monodisperse nanospheres of an intermetallic FeSn(5) phase via a nanocrystal-conversion protocol using preformed Sn nanospheres as templates. This tetragonal phase in P4/mcc space group, along with the defect structure Fe(0.74)Sn(5) of our nanospheres, has been resolved by synchrotron X-ray diffraction and Rietveld refinement. Importantly, FeSn(5), which is not yet established in the Fe-Sn phase diagram, exhibits a quasi-one dimensional crystal structure along the c-axis, thus leading to interesting anisotropic thermal expansion and magnetic properties. Magnetization measurements indicate that nanospheres are superparamagnetic above the blocking temperature T(B) = 300 K, which is associated with the higher magnetocrystalline anisotropy constant K = 3.33 kJ m(-3). The combination of the magnetization measurements and first-principles density functional theory calculations reveals the canted antiferromagnetic nature with significant spin fluctuation in lattice a-b plane. The low Fe concentration also leads Fe(0.74)Sn(5) to enhanced capacity as an anode in Li ion batteries.

Aligned CNx (x<0.1) nanotubes have been generated by pyrolyzing ferrocene/C60 mixtures at 1050 °C in an ammonia atmosphere. The structure and composition of the product were determined by high-resolution transmission electron microscopy and high spatial resolution electron energy-loss spectroscopy. The CNx tubes (15–70 nm diameter, <50 μm length) grown in large flakes (<3 mm2) consist of a reduced number of “graphitic” layers (<15 on either side) arranged in a bamboo-like structure. Areas of high nitrogen concentration were found within curved or corrugated “graphite-like” domains. The observation of a well-developed double peak in the σ* feature of the N K-edge suggests that the material has not undergone the transition to the fullerene-like phase known for nitrogenated carbons. Incorporation of nitrogen from the gas phase (NH3) into CNx nanotubes therefore leads to improved and more efficient N substitution into the network as compared to the synthesis with solid nitrogen-containing precursors reported earlier.

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