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Ferroelectric HfO2-based thin films have attracted much interest in the utilization of ferroelectricity at the nanoscale for next-generation electronic devices. However, the structural origin and stabilization mechanism of the ferroelectric phase are not understood because the film is typically nanocrystalline with active yet stochastic ferroelectric domains. Here, electron microscopy is used to map the in-plane domain network structures of epitaxially grown ferroelectric Y:HfO2 films in atomic resolution. The ferroelectricity is confirmed in free-standing Y:HfO2 films, allowing for investigating the structural origin for their ferroelectricity by 4D-STEM, high-resolution STEM, and iDPC-STEM. At the grain boundaries of <111>-oriented Pca21 orthorhombic grains, a high-symmetry mixed-(R3m, Pnm21) phase is induced, exhibiting enhanced polarization due to in-plane compressive strain. Nanoscale Pca21 orthorhombic grains and their grain boundaries with mixed-(R3m, Pnm21) phases of higher symmetry cooperatively determine the ferroelectricity of the Y:HfO2 film. It is also found that such ferroelectric domain networks emerge when the film thickness is beyond a finite value. Furthermore, in-plane mapping of oxygen positions overlaid on ferroelectric domains discloses that polarization is suppressed at vertical domain walls, while it is active when domains are aligned horizontally with subangstrom domain walls. In addition, randomly distributed 180° charged domain walls are confined by spacer layers.

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The development of white phosphors that can be activated in near-ultraviolet light is highly important in the field of LED lighting. In this work, a series of color-tunable Y2(Ti1-xHfx)2O7:Eu phosphors were prepared by adjusting the HfO2 and Eu3+ concentrations. In particular, white Y2(Ti0.8Hf0.2)2O7:Eu phosphors were successfully synthesized and emitted a broad band covering the entire visible light region upon excitation with 340 nm UV light. The white banded materials were composed of Eu2+ and Eu3+ emissions and HfO2 defect emission. The formation of Eu2+ ions was caused by the introduction of HfO2, which causes self-reduction of Eu3+ ions but does not require additional reducing agents. The white Y2(Ti0.8Hf0.2)2O7:Eu phosphors exhibit low color shifting at high temperature, which is very important for LED applications. The chromaticity shift of the Y2(Ti0.8Hf0.2)2O7:0.2Eu phosphor is 2.83 × 10-2 at 503 K, which is only 54.8 % that of commercial three-color white phosphors at the same temperature. The Ra value did not decrease significantly with increasing temperature and reached 90.2 at 383 K. Y2 (Ti0.8Hf0.2)2O7:0.2Eu phosphors were assembled with a 365 nm LED chip to fabricate a WLED device that showed excellent white-colored coordinates (0.345, 0.358) and a high Ra value of 90.1 under a 300 mA current.

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It is crucial for understanding mechanisms of drug action to quantify the three-dimensional (3D) drug distribution within a single cell at nanoscale resolution. Yet it remains a great challenge due to limited lateral resolution, detection sensitivities, and reconstruction problems. The preferable method is using X-ray nano-computed tomography (Nano-CT) to observe and analyze drug distribution within cells, but it is time-consuming, requiring specialized expertise, and often subjective, particularly with ultrasmall metal nanoparticles (NPs). Furthermore, the accuracy of batch data analysis through conventional processing methods remains uncertain. In this study, we used radioenhancer ultrasmall HfO2 nanoparticles as a model to develop a modular and automated deep learning aided Nano-CT method for the localization quantitative analysis of ultrasmall metal NPs uptake in cancer cells. We have established an ultrasmall objects segmentation method for 3D Nano-CT images in single cells, which can highly sensitively analyze minute NPs and even ultrasmall NPs in single cells. We also constructed a localization quantitative analysis method, which may accurately segment the intracellularly bioavailable particles from those of the extracellular space and intracellular components and NPs. The high bioavailability of HfO2 NPs in tumor cells from deeper penetration in tumor tissue and higher tumor intracellular uptake provide mechanistic insight into HfO2 NPs as advanced radioenhancers in the combination of quantitative subcellular image analysis with the therapeutic effects of NPs on 3D tumor spheroids and breast cancer. Our findings unveil the substantial uptake rate and subcellular quantification of HfO2 NPs by the human breast cancer cell line (MCF-7). This revelation explicates the notable efficacy and safety profile of HfO2 NPs in tumor treatment. These findings demonstrate that this 3D imaging technique promoted by the deep learning algorithm has the potential to provide localization quantitative information about the 3D distributions of specific molecules at the nanoscale level. This study provides an approach for exploring the subcellular quantitative analysis of NPs in single cells, offering a valuable quantitative imaging tool for minute amounts or ultrasmall NPs.

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Epitaxial strain plays an important role in the stabilization of ferroelectricity in doped hafnia thin films, which are emerging candidates for Si-compatible nanoscale devices. Here, we report on epitaxial ferroelectric thin films of doped HfO2 deposited on La0.7Sr0.3MnO3-buffered SrTiO3 substrates, La0.7Sr0.3MnO3 SrTiO3-buffered Si (100) wafers, and trigonal Al2O3 substrates. The investigated films appear to consist of four domains in a rhombohedral phase for films deposited on La0.7Sr0.3MnO3-buffered SrTiO3 substrates and two domains for those deposited on sapphire. These findings are supported by extensive transmission electron microscopy characterization of the investigated films. The doped hafnia films show ferroelectric behavior with a remanent polarization up to 25 µC/cm2 and they do not require wake-up cycling to reach the polarization, unlike the reported polycrystalline orthorhombic ferroelectric hafnia films.

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Logic-in-memory (LIM) architecture holds great potential to break the von Neumann bottleneck. Despite the extensive research on novel devices, challenges persist in developing suitable engineering building blocks for such designs. Herein, we propose a reconfigurable strategy for efficient implementation of Boolean logics based on a hafnium oxide-based ferroelectric field effect transistor (HfO2-based FeFET). The logic results are stored within the device itself (in situ) during the computation process, featuring the key characteristics of LIM. The fast switching speed and low power consumption of a HfO2-based FeFET enable the execution of Boolean logics with an ultralow energy of lower than 8 attojoule (aJ). This represents a significant milestone in achieving aJ-level computing energy consumption. Furthermore, the system demonstrates exceptional reliability with computing endurance exceeding 108 cycles and retention properties exceeding 1000 s. These results highlight the remarkable potential of a FeFET for the realization of high performance beyond the von Neumann LIM computing architectures.

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Recently discovered ferroelectricity in fluorite-structure ZrO2thin film has attracted increasing and intense interest due to its lower crystallization temperature and higher content in nature in comparison to hafnium oxide. Here, the effect of HfO2interfacial layer on the ferroelectric properties of ZrO2thin films is investigated systematically by designing four types of interfacial structures. It is revealed that the ferroelectric orthorhombic phase, remanent polarization, and endurance can be improved in ZrO2thin film by inserting both a top- and bottom-HfO2interfacial layer. A maximal ferroelectric remanent polarization (2Pr) of 53.4µC cm-2and an optimal endurance performance of 3 × 107field cycles under frequency of 100 kHz are achieved in Pt/HfO2/ZrO2/HfO2/Pt capacitors, with ferroelectric stacks being crystallized at 450 °C via post-deposition annealing method. X-ray photoelectron spectroscopy analysis confirms that the HfO2bottom-layer plays a very important role in the formation of a higher ratio o-phase, thus enhancing the ferroelectricity. These results suggest that designing appropriate interfaces would help achieve excellent ferroelectric properties in ZrO2films.

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Time-dependent second-harmonic generation (TD-SHG) is an emerging sensitive and fast method to qualitatively evaluate the interface quality of the oxide/Si heterostructures, which is closely related to the interfacial electric field. Here, the TD-SHG is used to explore the interface quality of atomic layer deposited HfO2 films on Si substrates. The critical SHG parameters, such as the initial SHG signal and characteristic time constant, are compared with the fixed charge density (Qox) and the interface state density (Dit) extracted from the conventional electrical characterization method. It reveals that the initial SHG signal linearly decreases with the increase in Qox, while Dit is linearly correlated to the characteristic time constant. It verifies that the TD-SHG is a sensitive and fast method, as well as simple and noncontact, for evaluating the interface quality of oxide/Si heterostructures, which may facilitate the in-line semiconductor test.

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Pioneering flexible micro-supercapacitors, designed for exceptional energy and power density, transcend conventional storage limitations. Interdigitated electrodes (IDEs) based on laser-induced graphene (LIG), augmented with metal-oxide modifiers, harness synergies with layered graphene to achieve superior capacitance. This study presents a novel one-step process for sputtered plasma deposition of HfO2, resulting in enhanced supercapacitance performance. Introducing LIG-HfO2 micro-supercapacitor (MSC) devices with varied oxygen flow rates further boosts supercapacitance performance by introducing oxygen functional groups. FESEM investigations demonstrate uniform coating of HfO2 on LIG fibers through sputtering. Specific capacitance measurements reveal 6.4 mF/cm2 at 5 mV/s and 4.5 mF/cm2 at a current density of 0.04 mA/cm2. The LIG-HfO2 devices exhibit outstanding supercapacitor performance, boasting at least a fourfold increase over pristine LIG. Moreover, stability testing indicates a high retention rate of 97% over 5000 cycles, ensuring practical real-time applications.

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High-performance thin films combining large optical bandgap Al2O3 and high refractive index HfO2 are excellent components for constructing the next generation of laser systems with enhanced output power. However, the growth of low-defect plasma-enhanced-atomic-layer-deposited (PEALD) Al2O3 for high-power laser applications and its combination with HfO2 and SiO2 materials commonly used in high-power laser thin films still face challenges, such as how to minimize defects, especially interface defects. In this work, substrate-layer interface defects in Al2O3 single-layer thin films, layer-layer interface defects in Al2O3-based bilayer and trilayer thin films, and their effects on the laser-induced damage threshold (LIDT) were investigated via capacitance-voltage (C-V) measurements. The experimental results show that by optimizing the deposition parameters, specifically the deposition temperature, precursor exposure time, and plasma oxygen exposure time, Al2O3 thin films with low defect density and high LIDT can be obtained. Two trilayer anti-reflection (AR) thin film structures, Al2O3/HfO2/SiO2 and HfO2/Al2O3/SiO2, were then prepared and compared. The trilayer AR thin film with Al2O3/HfO2/SiO2 structure exhibits a lower interface defect density, better interface bonding performance, and an increase in LIDT by approximately 2.8 times. We believe these results provide guidance for the control of interface defects and the design of thin film structures and will benefit many thin film optics for laser applications.

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Multifunctional integration in a single device has always been a hot research topic, especially for contradictory phenomena, one of which is the coexistence of ferroelectricity and metallicity. The complex oxide heterostructures, as symmetric breaking systems, provide a great possibility to incorporate different properties. Moreover, finding a series of oxide heterostructures to achieve this goal remains as a challenge. Here, taking the advantage of different physical phenomena, we use H2 plasma to pretreat the SrTiO3 (STO) substrate and then fabricate HfO2/STO heterostructures with it. The novel, well-repeatable metallic two-dimensional electron gas (2DEG) is directly obtained at the heterointerfaces without any further complex procedures, while the obvious ferroelectric-like behavior and Rashba spin-orbit coupling are also observed. The understanding of the mechanism, as well as the modified facile preparation procedure, would be meaningful for further development of ferroelectric metal in complex oxide heterostructures.

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The scale-free ferroelectricity with superior Si compatibility of HfO2 has reawakened the feasibility of scaled-down nonvolatile devices and beyond the complementary metal-oxide-semiconductor (CMOS) architecture based on ferroelectric materials. However, despite the rapid development, fundamental understanding, and control of the metastable ferroelectric phase in terms of oxygen ion movement of HfO2 remain ambiguous. In this study, we have deterministically controlled the orientation of a single-crystalline ferroelectric phase HfO2 thin film via oxygen ion movement. We induced a topotactic phase transition of the metal electrode accompanied by the stabilization of the differently oriented ferroelectric phase HfO2 through the migration of oxygen ions between the oxygen-reactive metal electrode and the HfO2 layer. By stabilizing different polarization directions of HfO2 through oxygen ion migration, we can gain a profound understanding of the oxygen ion-relevant unclear phenomena of ferroelectric HfO2.

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The gallium-doped hafnium oxide (Ga-HfO2) films with different Ga doping concentrations were prepared by adjusting the HfO2/Ga2O3 atomic layer deposition cycle ratio for high-speed and low-voltage operation in HfO2-based ferroelectric memory. The Ga-HfO2 ferroelectric films reveal a finely modulated coercive field (Ec) from 1.1 (HfO2/Ga2O3 = 32:1) to an exceptionally low 0.6 MV/cm (HfO2/Ga2O3 = 11:1). This modulation arises from the competition between domain nucleation and propagation speed during polarization switching, influenced by the intrinsic domain density and phase dispersion in the film with specific Ga doping concentrations. Higher Ec samples exhibit a nucleation-dominant switching mechanism, while lower Ec samples undergo a transition from a nucleation-dominant to a propagation-dominant reversal mechanism as the electric field increases. This work introduces Ga as a viable dopant for low Ec and offers insights into material design strategies for HfO2-based ferroelectric memory applications.

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Robust ferroelectricity in HfO2-based ultrathin films has the potential to revolutionize nonvolatile memory applications in nanoscale electronic devices because of their compatibility with the existing Si technology. However, to fully exploit the potential of ferroelectric HfO2-based thin films, it is crucial to develop strategies for the controlled stabilization of various HfO2-based polymorphs in nanoscale heterostructures. This study demonstrates how substrate-orientation-induced anisotropic strain can engineer the crystal symmetry, structural domain morphology, and growth orientation of ultrathin Hf0.5Zr0.5O2 (HZO) films. Epitaxial ultrathin HZO films were grown on the heterostructures of (001)- and (110)-oriented La2/3Sr1/3MnO3/SrTiO3 (LSMO/STO) substrate. Various structural analyses revealed that the (110)-oriented substrate promotes a higher degree of structural order (crystallinity) with improved stability of the (111)-oriented orthorhombic phase (Pca21) of HZO. Conversely, the (001)-oriented substrate not only induces a distorted orthorhombic structure but also facilitates the partial stabilization of nonpolar phases. Electrical measurements revealed robust ferroelectric properties in epitaxial thin films without any wake-up effect, where the well-ordered crystal symmetry stabilized by STO(110) facilitated better ferroelectric characteristics. This study suggests that tuning the epitaxial growth of ferroelectric HZO through substrate orientation can improve the stability of the metastable ferroelectric orthorhombic phase and thereby offer a better understanding of device applications.

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This research aimed to compare the quantitative imaging attributes of synthesized hafnium oxide nanoparticles (NPs) derived from UiO-66-NH2(Hf) and two gadolinium- and iodine-based clinical contrast agents (CAs) using cylindrical phantom. Aqueous solutions of the studied CAs, containing 2.5, 5, and 10 mg/mL of HfO2NPs, gadolinium, and iodine, were prepared. Constructed within a cylindrical phantom, 15 cc small tubes were filled with CAs. Maintaining constant mAs, the phantom underwent scanning at tube voltage variations from 80 to 140 kVp. The CT numbers were quantified in Hounsfield units (HU), and the contrast-to-noise ratios (CNR) were calculated within delineated regions of interest (ROI) for all CAs. The HfO2NPs at 140 kVp and concentration of 2.5 mg/ml exhibited 2.3- and 1.3-times higher CT numbers than iodine and gadolinium, respectively. Notably, gadolinium consistently displayed higher CT numbers than iodine across all exposure techniques and concentrations. At the highest tube potential, the maximum amount of the CAs CT numbers was attained, and at 140 kVp and concentration of 2.5 mg/ml of HfO2NPs the CNR surpassed iodine by 114%, and gadolinium by 30%, respectively. HfO2NPs, as a contrast agent, demonstrated superior image quality in terms of contrast and noise in comparison to iodine- and gadolinium-based contrast media, particularly at higher energies of X-ray in computed tomography. Thus, its utilization is highly recommended in CT.

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This study marks a significant stride in enhancing photoelectrochemical (PEC) water splitting applications through the development of a type II nano-heterojunction comprising HfO2 and α - Fe2O3. Fabricated via Physical Vapor Deposition/Radio Frequency (PVD/RF) sputtering, this nano-heterojunction effectively addresses the efficiency limitations inherent in traditional α - Fe2O3photoanodes. The integration of HfO2 leads to a substantial increase in photocurrent density, soaring from 62 µA/cm2 for pure α - Fe2O3 to 1.46 mA cm-2 at 1.23 V versus the Reversible Hydrogen Electrode (RHE). This enhancement, a 23-fold increase, is primarily attributed to the improved absorption of photons in the visible range and the facilitation of more efficient charge transfer. The enhanced performance and long-term stability of the HfO2/α - Fe2O3 nano-heterojunction, validated through XRD, XPS, Raman Spectroscopy, EDS, SEM, EIS, and UPS analyses, demonstrate its potential as a promising and cost-effective solution for PEC water splitting applications, leveraging renewable energy sources.

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SiGeSn nanocrystals (NCs) in oxides are of considerable interest for photo-effect applications due to the fine-tuning of the optical bandgap by quantum confinement in NCs. We present a detailed study regarding the silicon germanium tin (SiGeSn) NCs embedded in a nanocrystalline hafnium oxide (HfO2) matrix fabricated by using magnetron co-sputtering deposition at room temperature and rapid thermal annealing (RTA). The NCs were formed at temperatures in the range of 500-800 °C. RTA was performed to obtain SiGeSn NCs with surfaces passivated by the embedding HfO2 matrix. The formation of NCs and ß-Sn segregation were discussed in relation to the deposition and processing conditions by employing HRTEM, XRD and Raman spectroscopy studies. The spectral photosensitivity exhibited up to 2000 nm in short-wavelength infrared (SWIR) depending on the Sn composition was obtained. Comparing to similar results on GeSn NCs in SiO2 matrix, the addition of Si offers a better thermal stability of SiGeSn NCs, while the use of HfO2 matrix results in better passivation of NCs increasing the SWIR photosensitivity at room temperature. These results suggest that SiGeSn NCs embedded in an HfO2 matrix are a promising material for SWIR optoelectronic devices.

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The resistive switching property in HfO2have attracted increasing interest in recent years. In this work, amorphous HfO2nanocrystals are synthesized by a facile hydrothermal method. Then, the as-synthesized nanocrystals are rapid thermal annealed in different atmospheres for improving the crystal quality, and monoclinic phase is determined as the main crystal structure of the annealed HfO2. Subsequently, metal-insulator-metal structure devices based on HfO2samples are fabricated. Electrical measurement indicates that 700 °C annealing processes in Air and Ar environments can slightly improve the bipolar resistive switching and retention behaviors. Higher annealed temperature (900 °C) will further improve the crystal quality of HfO2, while the resistive switching and retention behaviors of the devices continuously attenuate, which can be ascribed to the reduction of the conductive filaments induced by defects.

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HfO2 shows promise for emerging ferroelectric and resistive switching (RS) memory devices owing to its excellent electrical properties and compatibility with complementary metal oxide semiconductor technology based on mature fabrication processes such as atomic layer deposition. Oxygen vacancy (Vo), which is the most frequently observed intrinsic defect in HfO2-based films, determines the physical/electrical properties and device performance. Vo influences the polymorphism and the resulting ferroelectric properties of HfO2. Moreover, the switching speed and endurance of ferroelectric memories are strongly correlated to the Vo concentration and redistribution. They also strongly influence the device-to-device and cycle-to-cycle variability of integrated circuits based on ferroelectric memories. The concentration, migration, and agglomeration of Vo form the main mechanism behind the RS behavior observed in HfO2, suggesting that the device performance and reliability in terms of the operating voltage, switching speed, on/off ratio, analog conductance modulation, endurance, and retention are sensitive to Vo. Therefore, the mechanism of Vo formation and its effects on the chemical, physical, and electrical properties in ferroelectric and RS HfO2 should be understood. This study comprehensively reviews the literature on Vo in HfO2 from the formation and influencing mechanism to material properties and device performance. This review contributes to the synergetic advances of current knowledge and technology in emerging HfO2-based semiconductor devices.

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Analog synaptic devices have made significant advances based on various electronic materials that can realize the biological synapse properties of neuromorphic computing. Ferroelectric (FE) HfO2-based materials with nonvolatile and low power consumption characteristics are being studied as promising materials for application to analog synaptic devices. The gradual reversal of FE multilevel polarization results in precise changes in the channel conductance and allows analogue synaptic weight updates. However, there have been few studies of FE synaptic devices doped with La, Y, and Gd. Furthermore, an investigation of interface quality is also crucial to enhance the remnant polarization (Pr), synaptic conductance linearity, and reliability characteristics. In this study, we demonstrate improved FE and artificial synaptic characteristics using an atomic layer-deposited (ALD) lanthanum-doped HfO2 (La:HfO2) and TaN electrode in the structure of an FE thin-film transistor (ITO/IGZO/La:HfO2/TaN), where indium-tin oxide (ITO) and indium-gallium-zinc oxide (IGZO) were used as source/drain and channel materials, respectively. Improved Pr and lower surface roughness were achieved by doped HfO2 and ALD TaN thin films. This synaptic transistor shows long-term potentiation and long-term depression with 200 levels of conductance states, high linearity (Ap, 0.97; Ad, 0.86), high Gmax/Gmin (∼6.1), and low cycle-to-cycle variability. In addition, a pattern recognition accuracy higher than 90% was achieved in an artificial neural network simulation.

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Hafnia-based nanostructures and other high-k dielectrics are promising wide-gap materials for developing new opto- and nanoelectronic devices. They possess a unique combination of physical and chemical properties, such as insensitivity to electrical and optical degradation, radiation damage stability, a high specific surface area, and an increased concentration of the appropriate active electron-hole centers. The present paper aims to investigate the structural, optical, and luminescent properties of anodized non-stoichiometric HfO2 nanotubes. As-grown amorphous hafnia nanotubes and nanotubes annealed at 700 °C with a monoclinic crystal lattice served as samples. It has been shown that the bandgap Eg for direct allowed transitions amounts to 5.65 ± 0.05 eV for amorphous and 5.51 ± 0.05 eV for monoclinic nanotubes. For the first time, we have studied the features of intrinsic cathodoluminescence and photoluminescence in the obtained nanotubular HfO2 structures with an atomic deficiency in the anion sublattice at temperatures of 10 and 300 K. A broad emission band with a maximum of 2.3-2.4 eV has been revealed. We have also conducted an analysis of the kinetic dependencies of the observed photoluminescence for synthesized HfO2 samples in the millisecond range at room temperature. It showed that there are several types of optically active capture and emission centers based on vacancy states in the O3f and O4f positions with different coordination numbers and a varied number of localized charge carriers (V0, V-, and V2-). The uncovered regularities can be used to optimize the functional characteristics of developed-surface luminescent media based on nanotubular and nanoporous modifications of hafnia.