Yang Yang#, Jijian Liu#, Chunyu Zhao#, Qingrong Liang, Weikang Dong, Jia Shi, Ping Wang, Denan Kong, Lu Lv, Lin Jia, Dainan Wang, Chun Huang, Shoujun Zheng, Meiling Wang, Fucai Liu, Peng Yu, Jingsi Qiao, Wei Ji, Jiadong Zhou*
Abstract:
The 2D ternary transition metal phosphorous chalcogenides (TMPCs) have attracted extensive research interest due to their widely tunable band gap, rich electronic properties, inherent magnetic and ferroelectric properties. However, the synthesis of TMPCs via chemical vapor deposition (CVD) is still challenging since it is difficult to control reactions among multi-precursors. Here, a subtractive element growth mechanism is proposed to controllably synthesize the TMPCs. Based on the growth mechanism, the TMPCs including FePS3, FePSe3, MnPS3, MnPSe3, CdPS3, CdPSe3, In2P3S9, and SnPS3 are achieved successfully and further confirmed by Raman, second-harmonic generation (SHG), and scanning transmission electron microscopy (STEM). The typical TMPCs–SnPS3 shows a strong SHG signal at 1064 nm, with an effective nonlinear susceptibility χ(2) of 8.41 × 10−11 m V−1, which is about 8 times of that in MoS2. And the photodetector based on CdPSe3 exhibits superior detection performances with responsivity of 582 mA W−1, high detectivity of 3.19 × 1011 Jones, and fast rise time of 611 µs, which is better than most previously reported TMPCs-based photodetectors. These results demonstrate the high quality of TMPCs and promote the exploration of the optical properties of 2D TMPCs for their applications in optoelectronics.
The quest for pragmatic room-temperature (RT) magnetic semiconductors (MSs) with a suitable bandgap constitutes one of the contemporary opportunities to be exploited. This may provide a materials platform for to bring new-generation ideal information device technologies into real-world applications where the otherwise conventionally separately utilized charge and spin are simultaneously exploited. Here we present RT ferromagnetism in an Fe-doped SnSe (Fe:SnSe) van der Waals (vdW) single crystalline ferromagnetic semiconductor (FMS) with a semiconducting bandgap of ∼1.19 eV (comparable to those of Si and GaAs). The synthesized Fe:SnSe single crystals feature a dilute Fe content of <1.0 at%, a Curie temperature of ∼310 K, a layered vdW structure nearly identical to that of pristine SnSe, and the absence of in-gap defect states. The Fe:SnSe vdW diluted magnetic semiconductor (DMS) single crystals are grown using a simple temperature-gradient melt-growth process, in which the magnetic Fe atom doping is realized uniquely using FeI2 as the dopant precursor whose melting point is low with respect to crystal growth, and which in principle possesses industrially unlimited scalability. Our work adds a new member in the family of long-searching RT magnetic semiconductors, and may establish a generalized strategy for large-volume production of related DMSs.
Abstract: Polymorphic structures of transition metal dichalcogenides (TMDs) host exotic electronic states, like charge density wave and superconductivity. However, the number of these structures is limited by crystal symmetries, which poses a challenge to achieving tailored lattices and properties both theoretically and experimentally. Here, we report a coloring triangle (CT) latticed MoTe2 monolayer, termed CT-MoTe2, constructed by controllably introducing uniform and ordered mirror-twin-boundaries into a pristine monolayer in molecular beam epitaxy. Low-temperature scanning tunneling microscopy and spectroscopy (STM/STS) together with theoretical calculations reveal that the monolayer has an electronic Janus lattice, i.e., an energy-dependent atomic-lattice and a Te pseudo-sublattice, and shares the identical geometry with the Mo5Te8 layer. Dirac-like and flat electronic bands inherently existing in the CT lattice are identified by two broad and two prominent peaks in STS spectra, respectively, and verified with density-functional-theory calculations. Two types of intrinsic domain boundaries were observed, one of which the electronic-Janus-lattice feature maintains, implying potential applications as an energy-tunable electron-tunneling barrier in future functional devices.
Negative Poisson’s ratio as the anomalous characteristic generally exists in artificial architectures, such as re-entrant and honeycomb structures. The structures with negative Poisson’s ratio have attracted intensive attention due to their unique auxetic effect and many promising applications in shear-resistant and energy absorption fields. However, experimental observation of negative Poisson’s ratio in natural materials barely happens, although various 2D layered materials are predicted in theory. Herein, the anisotropic Raman response and the intrinsic intralayer negative Poisson’s ratio of 2D natural black arsenic (b-As) via strain engineering strategy are reported. The results are evident by the detailed Raman spectrum of b-As under uniaxial strain together with density functional theory calculations. It is found that b-As is softer along the armchair than zigzag direction. The anisotropic mechanical features and van der Waals interactions play essential roles in strain-dependent Raman shifts and negative Poisson’s ratio in the natural b-As along zigzag direction. This work may shed a light on the mechanical properties and potential applications of 2D puckered materials.
Kagome-lattice materials possess attractive properties for quantum computing applications, but their synthesis remains challenging. Herein, based on the compelling identification of the two cleavable surfaces of Co3Sn2S2, we show surface kagome electronic states (SKESs) on a Sn-terminated triangular Co3Sn2S2 surface. Such SKESs are imprinted by vertical p-d electronic hybridization between the surface Sn (subsurface S) atoms and the buried Co kagome-lattice network in the Co3Sn layer under the surface. Owing to the subsequent lateral hybridization of the Sn and S atoms in a corner-sharing manner, the kagome symmetry and topological electronic properties of the Co3Sn layer is proximate to the Sn surface. The SKESs and both hybridizations were verified via qPlus non-contact atomic force microscopy (nc-AFM) and density functional theory calculations. The construction of SKESs with tunable properties can be achieved by the atomic substitution of surface Sn (subsurface S) with other group III-V elements (Se or Te), which was demonstrated theoretically. This work exhibits the powerful capacity of nc-AFM in characterizing localized topological states and reveals the strategy for synthesis of large-area transition-metal-based kagome-lattice materials using conventional surface deposition techniques.
