Van der Waals (vdW) layered materials have rather weaker interlayer bonding than the intra-layer bonding, therefore the exfoliation along the stacking direction enables the achievement of monolayer or few layers vdW materials with emerging novel physical properties and functionalities. The ferroelectricity in vdW materials recently attracts renewed interest for the potential use in high-density storage devices. As the thickness going thinner, the competition between the surface energy, depolarization field and interfacial chemical bonds may give rise to the modification of ferroelectricity and crystalline structure, which has limited investigations. In this work, combining the piezoresponse force microscope scanning, contact resonance imaging, we report the existence of the intrinsic in-plane polarization in vdW ferroelectrics CuInP2S6 (CIPS) single crystals, whereas below a critical thickness between 90-100 nm, the in-plane polarization disappears. The Young’s modulus also shows an abrupt stiffness at the critical thickness. Based on the density functional theory calculations, we ascribe these behaviors to a structural phase transition from monoclinic to trigonal structure, which is further verified by transmission electron microscope technique. Taken together, these findings demonstrate the foundational importance of structural phase transition for enhancing the rich functionality and broad utility of vdW ferroelectrics.

Published in: "arXiv Material Science".

As a fast-growing family of 2D materials, MXenes are rising into the limelight due to their attractive properties that leading to applications in energy storage, catalysis, microwave attenuation, etc. As their precursors, MAX phases are a family of layered, hexagonal-structure ternary carbides and nitrides. The exploration of novel MAX phases would largely expand the candidates for future MXenes with various component elements and microstructures. Meanwhile, apart from their indispensable role in Top-down synthesis of MXenes, MAX phase materials show remarkable combination of characteristics of metals and ceramics, endowing them great interest as both structural and functional materials. Up to now, there are more than 100 MAX compositions synthesized to date; and discoveries of new MAX phases (Ti3AuC2, Ti3IrC2, Ti2ZnC, Nb2CuC et al.) are continuously being reported by experimental scientists. To increase the efficiency in the successful search for novel MAX phases, a general guideline should be set up to direct experiment through an information-prediction system incorporating all MAX phases’ databases and high-quality regularities. In this work, we introduce the structure mapping methodology, which has shown its viability of being an effective guideline in design of MAX phases, and also provide simple principles for experimental scientists in the search for novel MAX phases. In fact, above-mentioned new MAX phases are falling into structure-stability regime that predicted by this structure mapping methodology. These new MAX phases, whatever experimentally reported or theoretically predicted, will largely enrich the structure-modification and property-tuning of derived MXenes.

Published in: "arXiv Material Science".