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Piezocatalysis, converting mechanical vibration into chemical energy, has emerged as a promising candidate for water-splitting technology. However, the efficiency of the hydrogen production is quite limited. We herein report well-defined 10 nm BaTiO3 nanoparticles (NPs) characterized by a large electro-mechanical coefficient which induces a high piezoelectric effect. Atomic-resolution high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and scanning probe microscopy (SPM) suggests that piezoelectric BaTiO3 NPs display a coexistence of multiple phases with low energy barriers and polarization anisotropy which results in a high electro-mechanical coefficient. Landau free energy modeling also confirms that the greatly reduced polarization anisotropy facilitates polarization rotation. Employing the high piezoelectric properties of BaTiO3 NPs, we demonstrate an overall water-splitting process with the highest hydrogen production efficiency hitherto reported, with a H2 production rate of 655 μmol g-1 h-1 , which could rival excellent photocatalysis system. This study highlights the potential of piezoelectric catalysis for overall water splitting.

Ferroelectric random-access memory (FRAM) based on conventional ferroelectric materials is a non-volatile memory with fast read/write operations, high endurance, and 10 years of data retention time. However, it suffers from destructive read-out operation and lack of CMOS compatibility. HfO2-based ferroelectric tunnel junctions (FTJ) may compensate for the shortcomings of FRAM by its CMOS compatibility, fast operation speed, and non-destructive readout operation. In this study, we investigate the effect of ferroelectric and interface film thickness on the tunneling electroresistance or ON/OFF current ratio of the Hf0.5Zr0.5O2/Al2O3based FTJ device. Integrating a thick ferroelectric layer (i.e. 12 nm Hf0.5Zr0.5O2) with a thin interface layer (i.e. 1 nm Al2O3) resulted in an ON/OFF current ratio of 78. Furthermore, to elucidate the relationship between ON/OFF current ratio and interfacial properties, the Hf0.5Zr0.5O2-Al2O3films and Ge-Al2O3interfaces are examined via time-of-flight secondary ion mass spectrometry depth profiling mode. A bilayer oxide heterostructure (Hf0.5Zr0.5O2/Al2O3) is deposited by atomic layer deposition (ALD) on the Ge substrate. The ON/OFF current ratio is enhanced by an order of magnitude when the Hf0.5Zr0.5O2film deposition mode is changed from exposure (H2O) ALD to sequential plasma (sequential O2-H2) ALD. Moreover, the interfacial engineering approach based on thein situALD H2-plasma surface pre-treatment of Ge increases the ON/OFF current ratio from 9 to 38 by reducing the interfacial trap density state at the Ge-Al2O3interface and producing Al2O3with fewer oxygen vacancies as compared to the wet etch (HF + H2O rinse) treatment of the Ge substrate. This study provides evidence of strong coupling between Hf0.5Zr0.5O2and Al2O3films in controlling the ON/OFF current ratio of the FTJ.

We introduce an Atomic Layer Deposition (ALD) technique referred to here as Sequential, No-Atmosphere Processing (SNAP) to fabricate ferroelectric Hf0.5Zr0.5O2 capacitors in Metal–Ferroelectric–Metal (MFM) structures. SNAP involves the ALD of each layer sequentially while maintaining the sample under vacuum process conditions without ambient exposure during the entire sequential deposition processes. We first use plasma enhanced ALD to fabricate 002-textured TiN films and study the degree of texture and quality of the film by X-ray Diffraction (XRD), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and transmission electron microscopy. Building upon the textured TiN film, we fabricate MFM capacitors with 10-nm-thick Hf0.5Zr0.5O2 via SNAP deposition and observe an unexpectedly large remanent polarization (2Pr = 54.2 μC/cm2). We report that annealing at T

Polymorphic (HfxZr1−x)O2 (HZO) thin films exhibit ferroelectric, dielectric, and antiferroelectric properties across a wide compositional range due to the existence of orthorhombic, monoclinic, and tetragonal phases. To better understand the phase stability across the HfO2–ZrO2 compositional range, we investigate the structural evolution of HZO thin films in situ via high-temperature x-ray diffraction (HTXRD) for five different compositions [ZrO2, (Hf0.23Zr0.77)O2, (Hf0.43Zr0.57)O2, (Hf0.67Zr0.33)O2, and HfO2]. The real-time monitoring of HZO crystallization reveals a competing driving force between the tetragonal and monoclinic phase stabilities for HfO2-rich vs ZrO2-rich compositions. Additionally, we confirm an XRD peak shift toward lower 2θ with increasing temperature in ZrO2, (Hf0.23Zr0.77)O2, and (Hf0.43Zr0.57)O2 films, which we ascribe to the appearance of a metastable orthorhombic phase during heating. A monotonic trend for the onset crystallization temperature is reported for five compositions of HZO and reveals an increase in onset crystallization temperature for HfO2-rich compositions. Relative intensity fraction calculations suggest a higher fraction of monoclinic phase with increasing annealing temperature for (Hf0.67Zr0.33)O2. This study of phase stability and onset crystallization temperatures offers insight for managing the thermal budget for HZO thin films, especially for temperature-constrained processing.

Hf0.5Zr0.5O2 (HZO) films are grown on rigid glass and flexible polyimide substrates using non-rapid thermal annealing. Films are comparatively investigated using macroscopic and local probe-based approaches to characterize their ferroelectric and piezoelectric properties. The polarization-electric field (P-E) measurements reveal that the ferroelectric characteristics of these thin films agree with the observed switchable piezoresponse hysteresis loops as well as electrically written, oppositely oriented domains. Moreover, the HZO thin films grown on flexible polyimide substrates display significantly enhanced piezoelectric response in comparison to the films grown on rigid substrates. This effect is likely due to improved domain wall motion caused by the mechanical release of the film-substrate couple. These findings suggest that inherently lead-free HZO thin films on flexible substrates are potential candidate materials for improved piezoelectric applications in wearable devices.