The family of 2D and layered materials has been expanding rapidly for more than a decade. Within this large family of hundreds of materials, black phosphorus and its isoelectronic group IV monochalcogenides have a unique place. These puckered materials have distinctive crystalline symmetries and exhibit various exciting properties, such as high carrier mobility, strong infrared responsivity, widely tunable bandgap, in-plane anisotropy and spontaneous electric polarization. Here, we review their basic properties, highlight new electronic and photonic device concepts and novel physical phenomena and discuss future directions.
The crystalline symmetries of layered black phosphorus and its isoelectronic group IV monochalcogenides play a very important role in the determination of their physical properties.
Black phosphorus is likely to be the layered semiconductor material with the highest carrier mobility at room temperature, making it promising for high-performance electronic applications.
Black phosphorus, arsenic phosphorus and other group V alloys may find applications in mid-infrared photonics as alternative material systems owing to their layered nature and moderate bandgap.
Monolayer group IV monochalcogenides have a broken inversion symmetry and spontaneous in-plane electric polarization. They present a great platform for the exploration of piezoelectricity, ferroelectricity, ferroelasticity and multiferroics.
In black phosphorus and other group V alloys, the interplay between the crystal symmetry and spin–orbit coupling may lead to the realization of rich topological states.
Wafer-scale synthesis of this group of materials remains challenging. Future research may leverage the phase transition induced by pressure, temperature or high-intensity light.
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The authors dedicate this manuscript to the memory of their wonderful mentor and collaborator, Mildred Dresselhaus of Massachusetts Institute of Technology, USA, who passed away in the planning stage of this Review. The authors are deeply indebted to her for her guidance, encouragement and support since the very early stage of research on BP and its related materials. Her warmness, generosity, great vision and unfailing optimism in science will always be remembered. F.X. acknowledges the financial and/or technical support from the Office of Naval Research, National Science Foundation, Air Force Office of Scientific Research, IBM Corporation and Yale University. L.Y. is thankful for support from the National Science Foundation, Air Force Office of Scientific Research and Washington University in St Louis. H.W. acknowledges support from the Army Research Office, Army Research Laboratory, Air Force Office of Scientific Research, National Science Foundation, Northrop Grumman Corporation and University of Southern California. J.H. acknowledges support from the Office of Naval Research, Air Force Office of Scientific Research and National Science Foundation. The authors thank T.-P. Ma and Y. Zhou at Yale University for helpful discussions on black phosphorus transistor scaling and MX synthesis, respectively.
F.X. has a pending patent application on the synthesis of encapsulated few-layer and thin-film black phosphorus and other group V compounds.
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Xia, F., Wang, H., Hwang, J.C.M. et al. Black phosphorus and its isoelectronic materials. Nat Rev Phys 1, 306–317 (2019). https://doi.org/10.1038/s42254-019-0043-5
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