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Hf0.5Zr0.5O2 (HZO) thin films are promising candidates for non-volatile memory and other related applications due to their demonstrated ferroelectricity at the nanoscale and compatibility with Si processing. However, one reason that HZO has not been fully scaled into industrial applications is due to its deleterious wake-up and fatigue behavior which leads to an inconsistent remanent polarization during cycling. In this study, we explore an interfacial engineering strategy in which we insert 1 nm Al2O3 interlayers at either the top or bottom HZO/TiN interface of sequentially deposited metal-ferroelectric-metal capacitors. By inserting an interfacial layer while limiting exposure to the ambient environment, we successfully introduce a protective passivating layer of Al2O3 that provides excess oxygen to mitigate vacancy formation at the interface. We report that TiN/HZO/TiN capacitors with a 1 nm Al2O3 at the top interface demonstrate a higher remanent polarization (2Pr ∼ 42 μC cm−2) and endurance limit beyond 108 cycles at a cycling field amplitude of 3.5 MV cm−1. We use time-of-flight secondary ion mass spectrometry, energy dispersive spectroscopy, and grazing incidence x-ray diffraction to elucidate the origin of enhanced endurance and leakage properties in capacitors with an inserted 1 nm Al2O3 layer. We demonstrate that the use of Al2O3 as a passivating dielectric, coupled with sequential ALD fabrication, is an effective means of interfacial engineering and enhances the performance of ferroelectric HZO devices.

Ferroelectric (Hf,Zr)O2 thin films have attracted increased interest from the ferroelectrics community and the semiconductor industry due to their ability to exhibit ferroelectricity at nanoscale dimensions. The properties and performance of the ferroelectric (Hf,Zr)O2 films generally depend on various factors such as surface energy (e.g., through grain size or thickness), defects (e.g., through dopants, oxygen vacancies, or impurities), electrodes, interface quality, and preferred crystallographic orientation (also known as crystallographic texture or simply texture) of grains and/or domains. Although some factors affecting properties and performance have been studied extensively, the effects of texture on the material properties are still not understood. Here, the influence of texture of the bottom electrode and Hf0.5Zr0.5O2 (HZO) films on properties and performance is reported. The uniqueness of this work is the use of a consistent deposition process known as Sequential, No-Atmosphere Processing (SNAP) that produces films with different preferred orientations yet minimal other differences. The results shown in this study provide both new insight on the importance of the bottom electrode texture and new fundamental processing-structure–property relationships for the HZO films.

In this work, a new surface engineering technique through UV/ozone treatment to improve the oxygen evolution reaction performance of nickel-iron hydroxide based catalysts has been developed. It is found that UV/ozone treatment can significantly improve the hydrophilicity of the catalysts as well as modify the electronic structure at the Ni–Fe center and oxidize Ni2+ to Ni3+, which consequently enables better electrode–electrolyte contacts, stronger charge-transfer and more numbers of active sites with higher intrinsic activity during the OER. This work demonstrates UV/ozone treatment as a highly effective strategy towards the rational design of high-performance electrocatalysts by exploiting surface modifications.

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. HfO

HfO2-based antiferroelectric-like thin films are increasingly being considered for commercial devices. However, even with initial promise, the temperature sensitivity of electrical properties such as loss tangent and leakage current remains unreported. 50 nm thick, 4 at. % Al-doped HfO2 thin films were synthesized via atomic layer deposition with both top and bottom electrodes being TiN or Pt. A study of their capacitance vs temperature showed that the Pt/Al:HfO2/Pt had a relative dielectric permittivity of 23.30 ± 0.06 at room temperature with a temperature coefficient of capacitance (TCC) of 78 ± 86 ppm/°C, while the TiN/Al:HfO2/TiN had a relative dielectric permittivity of 32.28 ± 0.14 at room temperature with a TCC of 322 ± 41 ppm/°C. The capacitance of both devices varied less than 6% over 1 to 1000 kHz from −125 to 125 °C. Both capacitors maintained loss tangents under 0.03 and leakage current densities of 10−9–10−7 A/cm2 between −125 and 125 °C. The TiN/Al:HfO2/TiN capacitor maintained an energy storage density (ESD) of 18.17 ± 0.79 J/cm3 at an efficiency of 51.79% ± 2.75% over the −125 to 125 °C range. The Pt/Al:HfO2/Pt capacitor also maintained a stable ESD of 9.83 ± 0.26 J/cm3 with an efficiency of 62.87% ± 3.00% over the same temperature range. Such low losses in both capacitors along with their thermal stability make antiferroelectric-like, Al-doped HfO2 thin films a promising material for temperature-stable microelectronics.

In the United States many women in science, technology, engineering, and mathematics (STEM) leave their careers after becoming a parent. Attrition is simultaneously occurring with workforce shortages in STEM with two million jobs potentially unfilled by 2025. While there has been an increase in STEM recruitment of women over recent decades, policies aimed at decreasing departure of women in STEM have not been prioritized. The Family and Medical Leave Act of 1993 (FMLA) guarantees workers up to 12 weeks of unpaid, job-protected leave, but has not shown to increase workforce attachment of new mothers. Instead, studies suggest that short durations of paid leave (6-12 weeks) increase workforce attachment. Medical consensus suggests that a leave of 26 weeks is necessary for maternal health and a leave of 40 weeks is optimal for infant well-being. Coupled with recently introduced paid parental leave legislation in Congress, we recommend timely action to decrease the departure of women from the workforce and to strengthen gender equality in STEM. We recommend instituting 12 weeks of federal paid family leave (PFL) under the recently introduced national family leave insurance program in the Family and Medical Insurance Leave Act (FAMILY Act; S. 463/H.R. 1185).

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.