Recent Advances in 2D Group VB Transition Metal Chalcogenides.

2D materials have received considerable research interest owing to their abundant material systems and remarkable properties. Among them, 2D group VB transition metal chalcogenides (GVTMCs) stand out as emerging 2D metallic materials and significantly broaden the research scope of 2D materials. 2D GVTMCs have great advantages in electrical transport, 2D magnetism, charge density wave, sensing, catalysis, and charge storage, making them attractive in the fields of functional devices and energy chemistry. In this review, the recent progress of 2D GVTMCs is summarized systematically from fundamental properties, growth methodologies to potential applications. The challenges and prospects are also discussed for future research in this field.

Synergistic Additive-Assisted Growth of 2D Ternary In2 SnS4 with Giant Gate-Tunable Polarization-Sensitive Photoresponse.

2D ternary materials exhibit great promise in the field of polarization-sensitive photodetectors due to the low-symmetry crystal structure. However, the realization of ternary material growth is still a huge challenge because of the complex reaction process. Here, for the first time, 2D ternary In2 SnS4 flakes are obtained via synergistic additive of salt and molecular sieve-assisted chemical vapor deposition. Raman vibration mode of In2 SnS4 flakes exhibits polarization-dependent properties. The polarization-resolved absorption spectroscopy and azimuth-dependent reflectance difference microscopy further confirm its anisotropy of in-plane optical absorption and reflection. Besides, the In2 SnS4 flake based device on mica shows ultrafast rising and decay rates of ≈20 and 20 µs. Impressively, In2 SnS4 flake based phototransistor demonstrates giant gate-tunable polarization-sensitive photoresponse: the dichroic ratio can be adjusted in the range of 1.13-1.70 with gate voltage varying from -35-35 V. This work provides an effective means for modulating the polarization-sensitive photoresponse, which may significantly promote the research progress of polarization-sensitive photodetectors.

Structural Determination and Nonlinear Optical Properties of New 1T‴-Type MoS2 Compound.

Noncentrosymmetric MoS2 semiconductors (1H, 3R) possess not only novel electronic structures of spin-orbit coupling (SOC) and valley polarization but also remarkable nonlinear optical effects. A more interesting noncentrosymmetric structure, the so-called 1T‴-MoS2 layers, was predicted to be built up from [MoS6] octahedral motifs by theoreticians, but the bulk 1T‴ MoS2 or its single crystal structure has not been reported yet. Here, we have successfully harvested 1T‴ MoS2 single crystals by a topochemical method. The new layered structure is determined from single-crystal X-ray diffraction. The crystal crystallizes in space group P31m with a cell of a = b = 5.580(2) Å and c = 5.957(2) Å, which is a √3 a × âˆš3 a superstructure of 1T MoS2 with corner-sharing Mo3 triangular trimers observed by the STEM. 1T‴ MoS2 is verified to be semiconducting and possesses a band gap of 0.65 eV, different from metallic nature of 1T or 1T' MoS2. More surprisingly, the 1T‴ MoS2 does show strong optical second-harmonic generation signals. This work provides the first layered noncentrosymmetric semiconductor of edge-sharing MoS6 octahedra for the research of nonlinear optics.

Halide-Induced Self-Limited Growth of Ultrathin Nonlayered Ge Flakes for High-Performance Phototransistors.

2D nonlayered materials have attracted intensive attention due to their unique surface structure and novel physical properties. However, it is still a great challenge to realize the 2D planar structures of nonlayered materials owing to the naturally intrinsic covalent bonds. Ge is one of them with cubic structure impeding its 2D anisotropic growth. Here, the ultrathin single-crystalline Ge flakes as thin as 8.5 nm were realized via halide-assisted self-limited CVD growth. The growth mechanism has been confirmed by experiments and theoretical calculations, which can be attributed to the preferential growth of the (111) plane with the lowest formation energy and the giant interface distortion effect of the Cl-Ge motif. Excitingly, a Ge flake-based phototransistor shows excellent performances such as a high hole mobility of ∼263 cm2 V-1 s-1, a high responsivity of ∼200 A/W, and fast response rates (τrise = 70 ms, τdecay = 6 ms), suggesting its great potential in the applications of electronics and optoelectronics.

Temperature dependence of Raman responses of few-layer PtS2.

Platinum disulfide (PtS2) is a newly emerging 2D material, which possesses relatively high carrier mobility, a widely tunable band gap from 0.25 to 1.6 eV, and ultra-high air stability, showing a potential in electronics and optoelectronics. Here, for the first time, we study the temperature-dependent Raman spectra on PtS2 with different thicknesses. It was found that with the temperature increase from 80 to 298 K, the [Formula: see text] and [Formula: see text] modes of all samples show linear softening. Moreover, the linear softening with temperature of PtS2 is much smaller than other 2D transition metal dichalcogenides, which could be attributed to the stronger interlayer coupling in PtS2. Our work gives fundamental temperature-dependent vibrational information of PtS2, which will be useful in future PtS2-based electronic devices.

Circularly polarized luminescence enlargement from crystals to oriented films of enantiopure 2D hybrid perovskites.

Chiral 2D organic-inorganic hybrid perovskites (C-2D-OIHPs) with circularly polarized luminescence (CPL) have important promising applications in optical, electronic, and chiroptoelectronic devices. Herein, we report enantiomeric crystals of R/S-FMBA)2PbBr4. (FMBA = 4-fluorophenethylamine), which demonstrated bright room-temperature CPL emission. For the first time, the oriented films along the c-axis of this pair of C-2D-OIHPs exhibited a 16-fold increase in the asymmetry factors of absorbance (gCD) and a 5-fold rise in the asymmetry factors of CPL (glum), reaching up to ± 1 × 10-2.

Epitaxial coordination assembly of a semi-conductive silver-chalcogenide layer-based MOF.

Using a carboxylic acid linker, this work achieved the epitaxially coordinated assembly of a Ag-S layer into a three-dimensional semi-conductive framework, with high thermal stability, as well as an interesting temperature-dependent luminescence response. This work provides a new avenue to prepare semi-conductive metal-chalcogenide layer-based materials in electricity-related applications.

Recent Advances in 2D Layered Phosphorous Compounds.

2D layered phosphorous compounds (2D LPCs) have led to explosion of research interest in recent years. With the diversity of valence states of phosphorus, 2D LPCs exist in various material types and possess many novel physical and chemical properties. These properties, including widely adjustable range of bandgap, diverse electronic properties covering metal, semimetal, semiconductor and insulator, together with inherent magnetism and ferroelectricity at atomic level, render 2D LPCs greatly promising in the applications of electronics, spintronics, broad-spectrum optoelectronics, high-performance catalysts, and energy storage, etc. In this review, the recently research progress of 2D LPCs are presented in detail. First, the 2D LPCs are classified according to their elemental composition and the corresponding crystal structures are introduced, followed by their preparation methods. Then, the novel properties are summarized and the potential applications are discussed in detail. Finally, the conclusion and perspective of the promising 2D LPCs are discussed on the foundation of the latest research progress.

A Self-Powered Photovoltaic Photodetector Based on a Lateral WSe2-WSe2 Homojunction.

Lateral homojunctions made of two-dimensional (2D) layered materials are promising for optoelectronic and electronic applications. Here, we report the lateral WSe2-WSe2 homojunction photodiodes formed spontaneously by thickness modulation in which there are unique band structures of a unilateral depletion region. The electrically tunable junctions can be switched from n-n to p-p diodes, and the corresponding rectification ratio increases from about 1 to 1.2 × 104. In addition, an obvious photovoltaic behavior is observed at zero gate voltage, which exhibits a large open voltage of 0.49 V and a short-circuit current of 0.125 nA under visible light irradiation. In addition, due to the unilateral depletion region, the diode can achieve a high detectivity of 4.4 × 1010 Jones and a fast photoresponse speed of 0.18 ms at Vg = 0 and Vds = 0. The studies not only demonstrated the great potential of the lateral homojunction photodiodes for a self-power photodetector but also allowed for the development of other functional devices, such as a nonvolatile programmable diode for logic rectifiers.

Large-Scale Ultrathin 2D Wide-Bandgap BiOBr Nanoflakes for Gate-Controlled Deep-Ultraviolet Phototransistors.

Ternary two-dimensional (2D) semiconductors with controllable wide bandgap, high ultraviolet (UV) absorption coefficient, and critical tuning freedom degree of stoichiometry variation have a great application prospect for UV detection. However, as-reported ternary 2D semiconductors often possess a bandgap below 3.0 eV, which must be further enlarged to achieve comprehensively improved UV, especially deep-UV (DUV), detection capacity. Herein, sub-one-unit-cell 2D monolayer BiOBr nanoflakes (≈0.57 nm) with a large size of 70 µm are synthesized for high-performance DUV detection due to the large bandgap of 3.69 eV. Phototransistors based on the 2D ultrathin BiOBr nanoflakes deliver remarkable DUV detection performance including ultrahigh photoresponsivity (Rλ , 12739.13 A W-1 ), ultrahigh external quantum efficiency (EQE, 6.46 × 106 %), and excellent detectivity (D*, 8.37 × 1012 Jones) at 245 nm with a gate voltage (Vg ) of 35 V attributed to the photogating effects. The ultrafast response (τrise = 102 µs) can be achieved by utilizing photoconduction effects at Vg of -40 V. The combination of photocurrent generation mechanisms for BiOBr-based phototransistors controlled by Vg can pave a way for designing novel 2D optoelectronic materials to achieve optimal device performance.

Salt-Assisted Growth of Ultrathin GeSe Rectangular Flakes for Phototransistors with Ultrahigh Responsivity.

Two-dimensional (2D) GeSe is an important IVA-VIA semiconductor for future applications in electronics and optoelectronics because of its high absorption coefficient, mobility, and photoresponsivity. However, the controllable synthesis of 2D GeSe flakes is still a huge problem. Here, high-quality single-crystalline ultrathin 2D GeSe flakes are synthesized by a salt-assisted chemical vapor deposition method. The flakes tend to grow along the [010] crystal orientation presenting a rectangular shape with a thickness down to 5 nm. Then, the electrical and optoelectronic properties have been systematically investigated. A thickness-dependent Schottky barrier is shown in GeSe field-effect transistors. The p-type conductivity of GeSe is mainly caused by the Ge deficiency, which is proven by a variable-temperature experiment and theoretical calculations. In addition, the phototransistors based on as-grown GeSe flakes present an ultrahigh responsivity of 1.8 × 104 A/W and an excellent external quantum efficiency of 4.2 × 106%.

Self-Confined Growth of Ultrathin 2D Nonlayered Wide-Bandgap Semiconductor CuBr Flakes.

2D planar structures of nonlayered wide-bandgap semiconductors enable distinguished electronic properties, desirable short wavelength emission, and facile construction of 2D heterojunction without lattice match. However, the growth of ultrathin 2D nonlayered materials is limited by their strong covalent bonded nature. Herein, the synthesis of ultrathin 2D nonlayered CuBr nanosheets with a thickness of about 0.91 nm and an edge size of 45 µm via a controllable self-confined chemical vapor deposition method is described. The enhanced spin-triplet exciton (Zf , 2.98 eV) luminescence and polarization-enhanced second-harmonic generation based on the 2D CuBr flakes demonstrate the potential of short-wavelength luminescent applications. Solar-blind and self-driven ultraviolet (UV) photodetectors based on the as-synthesized 2D CuBr flakes exhibit a high photoresponsivity of 3.17 A W-1 , an external quantum efficiency of 1126%, and a detectivity (D*) of 1.4 × 1011 Jones, accompanied by a fast rise time of 32 ms and a decay time of 48 ms. The unique nonlayered structure and novel optical properties of the 2D CuBr flakes, together with their controllable growth, make them a highly promising candidate for future applications in short-wavelength light-emitting devices, nonlinear optical devices, and UV photodetectors.

Highly Anisotropic GeSe Nanosheets for Phototransistors with Ultrahigh Photoresponsivity.

2D GeSe possesses black phosphorous-analog-layered structure and shows excellent environmental stability, as well as highly anisotropic in-plane properties. Additionally, its high absorption efficiency in the visible range and high charge carrier mobility render it promising for applications in optoelectronics. However, most reported GeSe-based photodetectors show frustrating performance especially in photoresponsivity. Herein, a 2D GeSe-based phototransistor with an ultrahigh photoresponsivity is demonstrated. Its optimized photoresponsivity can be up to ≈1.6 × 105 A W-1. This high responsivity can be attributed to the highly efficient light absorption and the enhanced photoconductive gain due to the existence of trap states. The exfoliated GeSe nanosheet is confirmed to be along the [001] (armchair direction) and [010] (zigzag direction) using transmission electron microscopy and anisotropic Raman characterizations. The angle-dependent electric and photoresponsive performance is systematically explored. Notably, the GeSe-based phototransistor shows strong polarization-dependent photoresponse with a peak/valley ratio of 1.3. Furthermore, the charge carrier mobility along the armchair direction is measured to be 1.85 times larger than that along the zigzag direction.

Tunneling Diode Based on WSe2 /SnS2 Heterostructure Incorporating High Detectivity and Responsivity.

van der Waals (vdW) heterostructures based on atomically thin 2D materials have led to a new era in next-generation optoelectronics due to their tailored energy band alignments and ultrathin morphological features, especially in photodetectors. However, these photodetectors often show an inevitable compromise between photodetectivity and photoresponsivity with one high and the other low. Herein, a highly sensitive WSe2 /SnS2 photodiode is constructed on BN thin film by exfoliating each material and manually stacking them. The WSe2 /SnS2 vdW heterostructure shows ultralow dark currents resulting from the depletion region at the junction and high direct tunneling current when illuminated, which is confirmed by the energy band structures and electrical characteristics fitted with direct tunneling. Thus, the distinctive WSe2 /SnS2 vdW heterostructure exhibits both ultrahigh photodetectivity of 1.29 × 1013 Jones (Iph /Idark ratio of ≈106 ) and photoresponsivity of 244 A W-1 at a reverse bias under the illumination of 550 nm light (3.77 mW cm-2 ).