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Enhanced Spontaneous Polarization in Ultrathin SnTe Films with Layered Antipolar Structure

2D SnTe films with a thickness of as little as 2 atomic layers (ALs) have recently been shown to be ferroelectric with in–plane polarization. Remarkably, they exhibit transition temperatures (T c ) much higher than that of bulk SnTe. Here, combining molecular beam epitaxy, variable temperature scanning tunneling microscopy, and ab initio calculations, the underlying mechanism of the Tc enhancement is unveiled, which relies on the formation of γ–SnTe, a van der Waals orthorhombic phase with antipolar inter–layer coupling in few–AL thick SnTe films. In this phase, 4n – 2 AL (n = 1, 2, 3…) thick films are found to possess finite in–plane polarization (space group Pmn2 1 ), while 4n AL thick films have zero total polarization (space group Pnma). Above 8 AL, the γ–SnTe phase becomes metastable, and can convert irreversibly to the bulk rock salt phase as the temperature is increased. This finding unambiguously bridges experiments on ultrathin SnTe films with predictions of robust ferroelectricity in GeS–type monochalcogenide monolayers. Here, the observed high transition temperature, together with the strong spin–orbit coupling and van der Waals structure, underlines the potential of atomically thin γ–SnTe films for the development of novel spontaneous polarization–based devices.

2d ferroelectrics↗

Characterization, Structure, and Reactivity of Hydroxyl Groups on Metal‐Oxide Cluster Nodes of Metal–Organic Frameworks: Structural Diversity and Keys to Reactivity and Catalysis

Among the most stable metal–organic frameworks (MOFs) are those incorporating nodes that are metal oxide clusters with frames such as Zr 6 O 8 . This review is a summary of the structure, bonding, and reactivity of MOF node hydroxyl groups, emphasizing those bonded to nodes containing aluminum and zirconium ions. Hydroxyl groups are often present on these nodes, sometimes balancing the charges of the metal ions. They arise during MOF syntheses in aqueous media or in post-synthesis treatments. They are identified with infrared and 1 H nuclear magnetic resonance spectroscopies and characterized by their reactivities with polar compounds such as alcohols. Terminal OH, paired µ 2 -OH, and aqua groups on nodes are catalytic sites in numerous reactions. Relatively unreactive hydroxyl groups (such as isolated µ 2 -OH groups) may replace reactive groups and inhibit catalysis; some node hydroxyl groups (e.g., µ 3 -OH) are mere spectators in catalysis. There are similarities between MOF node hydroxyl groups and those on the surfaces of bulk metal oxides, zeolites, and enzymes, but the comparisons are mostly inexact, and much remains to be understood about MOF node hydroxyl group chemistry. It is posited that understanding and controlling this chemistry will lead to tailored MOFs and improved adsorbents and catalysts.

36 MATERIALS SCIENCE↗