Ferroelectric Hf0.5Zr0.5O2 films, 5.8 nm in thickness, were deposited on Nb:SrTiO3 semiconductor substrates to form a Pt/Hf0.5Zr0.5O2/Nb:SrTiO3 metal/ferroelectric/semiconductor ferroelectric tunnel junction (FTJ). A high tunneling electroresistance ratio of 800 was achieved at room-temperature. It is observed that in the low resistance state, the transport characteristic obeys direct tunneling, while in the high resistance state, it is dominated by thermal emission. It implies that the Schottky barrier on the surface of the semiconductive electrode is modulated by the polarization in the ferroelectric Hf0.5Zr0.5O2 barrier, generating the high electroresistance ratio. The FTJ also exhibits excellent retention for more than 10 000 s and good switching endurance for more than 1500 cycles. The results suggest the potential of this HfO2-based FTJ for next generation nonvolatile memories.
Hf0.5Zr0.5O2 (HZO) thin films have been deposited on (110)-oriented SrTiO3 (STO) substrates buffered with epitaxial La0.7Sr0.3MnO3 (LSMO) by pulsed laser deposition. The HZO/LSMO/STO heterostructures show smooth surface and clear interface. It is observed that ferroelectric orthorhombic HZO is enhanced, as non-polar tetragonal HZO is suppressed with the increasing LSMO thickness or decreasing HZO thickness. Completely orthorhombic HZO films are achieved with desired LSMO and HZO thickness. These HZO films are (111)-oriented with in-plane [2¯11] and [01¯1] directions along LSMO [11¯0] and [001], respectively, and exhibit ferroelectric properties at room temperature with an optimized remanent polarization around 26 μC/cm2 without the need of a wake-up process, a long retention up to 104 s and a fatigue endurance up to 109 cycles. Epitaxial HfO2-based films with robust ferroelectric properties deposited on (110)-oriented STO substrates provide additional opportunities to understand the profound effects of orientation, strain, and interface microstructures on the metastable polar phases and ferroelectric properties of HfO2 thin films.
Organic-inorganic hybrid ferroelectrics (OIHFs) have fueled enormous interest benefiting from their less environmental pollution, performance-tailored functionality, low product costs as well as tunability of structures. However, the lack of material synthesis approaches and diverse targeted molecular design is a stumbling block for designing novel OIHFs rationally. Here, we report a unique organic-inorganic hybrid ferroelectric (3,3-difluoropyrrolidine)2CdCl4 1 and another novel nonferroelectric crystal (3,3-difluoropyrrolidine)2Cd2Cl6 2 by changing various crystallization solvents. Significantly, 1 presents a ferroelectric phase transition behavior at ∼367 K, and the distinct symmetry breaking, i.e., mmmFm, sets up a biaxial ferroelectric with four equivalent directions of polarization, which has a P r ∼ 0.77 μC/cm2. Systematic studies prove that ferroelectricity can be ascribed to the synergistic effects of the distortion of the inorganic anion skeleton and the ordering of organic cations. This work reveals the potential of constructing novel ferroelectrics based on the solvent selective effect and pyrrolidinium as organic cations.
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