HfO2 Research Articles

Abstract 2973: Analysis of NBTXR3 nanoparticles recapture after release by dying cells

Abstract In 2011, NBTXR3 emerged as the pioneering radioenhancer used in clinical practice to treat patients with locally advanced soft tissue sarcoma (LA-STS). Following the successful completion of a phase II/III clinical study for LA-STS, with a doubling of the pCR rate in the NBTXR3 arm compared with the control arm. NBTXR3 became the first radioenhancer to receive CE mark approval. NBTXR3 nanoparticles are composed of a functionalized core made of hafnium oxide, a high atomic number element. They were designed to enhance the effects of radiotherapy (RT) within cells without causing additional side effects on healthy tissues. Exploiting this physical mechanism, radiation-activated NBTXR3 (NBTXR3+RT) has exhibited superior efficacy in eradicating tumor cells and managing tumor growth in various preclinical models and in human studies. It surpasses the effects of RT alone while maintaining a favorable safety profile. Recent preclinical investigations have uncovered that the advantages of NBTXR3 go beyond mere radioenhancement and improved cancer cell destruction. Notably, NBTXR3 has been reported to possess immunomodulatory properties through several mechanisms, including 1) improved induction of DNA damage, leading to enhanced activation of the cGAS-STING pathway, 2) promotion of immunogenic cell death, 3) enhancement of immunopeptidome presentation, 4) generation of an antitumor immune response that results in the production of an abscopal effect mediated by CD8+ cytotoxic lymphocytes. Significantly, a series of recent studies using a two-tumor mouse model of anti-PD1-resistant lung cancer demonstrated that the addition of NBTXR3 significantly improved the efficacy of various treatment regimens (combinations of RT plus anti-PD1 and other checkpoint inhibitors) in terms of tumor growth, abscopal effect, and overall survival. Furthermore, similar benefits can be achieved when NBTXR3 is combined with proton therapy (PBT). Moreover, all these studies (both X-ray and PBT) reported a robust activation of the antitumor immune response, the restoration of the effectiveness of anti-PD1 therapy, and the induction of a memory response in cured mice. But our knowledge of the underlying biological processes that lead to these effects remains rather limited. For example, no information is available about the fate of these nanoparticles once they are injected into a tumor or when they are released by dying cancer cells. To gain a better understanding of these issues, we conducted a series of in vitro and in vivo experiments. We demonstrate that the endocytosis occurs similarly both in vivo and in vitro, at the level of tumor cells. Furthermore, we demonstrate in vitro that nanoparticles taken up by these tumor cells and subsequently released upon their death can be reinternalized by other tumor cells, thus facilitating their destruction by RT. These initial findings provide a deeper insight into the behavior of NBTXR3. Citation Format: Jordan Da silva, Célia Bienassis, Sebastien Paris. Analysis of NBTXR3 nanoparticles recapture after release by dying cells [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 2973.

Investigation of spacer-engineered stacked nanosheet tunnel FET with varying design attributes

The stacked nanosheet field-effect transistors (SNS-FETs) are potential contenders for sub-7 nm technology. Device miniaturization leads to a larger off-state current and a higher subthreshold slope in SNS-FETs. Unlike SNS-FETs, the stacked nanosheet tunnelling field effect transistors (SNS-TFETs) function as switches in integrated circuits, featuring high performance and low power consumption. The endeavour aims to investigate how each design parameter optimises the switching characteristics of the SNS-TFET device. This paper examines various design attributes, such as different dielectric spacer materials, nanosheet width (NW), nanosheet thickness (NT), source doping, drain doping, etc. The Cogenda Visual TCAD serves as a tool for conducting device simulations. According to the simulation study, the use of a high-k hafnium dioxide (HfO2) spacer produces a higher switching ratio ( 7.28×1011 ) and a lower subthreshold swing (20.303 mV/decade). Using either low-k or no spacers reduces the overall gate capacitance and unit frequency gain compared to high-k spacers. Upscaling the nanosheet width (10 to 50 nm) enhances the switching ratio by 1.11×101 and transconductance by 61.92%. Downscaling the nanosheet thickness (6 to 4 nm) at the optimized nanosheet width (50 nm) improves the switching ratio by 1.88. Increasing the gate length from 8 to 16 nm reduces the leakage current by 2.34×10−2 A and improves the switching ratio by 2.90×101. An increase in the source doping level from 1×1020 to 5×1020 cm−3 results in a 1.07×102 decrease in the switching ratio and a 2.48-fold increase in the subthreshold swing. Furthermore, the findings indicate that drain doping is crucial in determining ambipolar current. In SNS-TFET, ambipolar current reduces significantly when drain doping is 1×1017 cm−3. Thus, the proposed work addresses the limitations of scaling and optimised design parameter characteristics for low-power nanoscale circuits.

Water Dose influence to the ALD hafnium oxide process: Simulation and experiment

In this work, we report a two-dimensional gas-dynamic model for the formation of hafnium oxide from TDMAH and water during the atomic layer deposition (ALD) process. Application of the model is demonstrated by the example of water cycle, in which the monolayer of functional groups –OH is formed. The simulation results show that the duration of the water pulse affects the dynamics of surface coverage with the -OH groups. At short pulse durations, the resulting coverage of the film surface with -OH groups becomes incomplete and has heterogeneous distribution over the film surface, which is due to the design of the reaction chamber and regimes of gas supply. The amount of residual water vapor depends on the duration of the water pulse and pumping regimes. Experimental data show the influence of water pulse duration on the refractive index, which is related to the structure of the deposited layer (composition, morphology, etc.). Based on experimental data and modeling results, we explain the effect of water pulse duration on the refractive index by the change in reaction mechanisms depending on water amount in the chamber. With a lack of water, the incomplete monolayer of –OH groups is formed and a {HfO2-y} layer grows as a result of the monomolecular decomposition of the precursor. With an excess of water, we expect the implementation of multilayer adsorption of water, provoking the reaction of the precursor in the volume of the water film, leading to the formation of the product {HfO2+y}.

CONDUCTIVITY OF HAFNIUM OXIDE LMS OBTAINED BY ELECTRON BEAM SPUTTERING

Films of hafnium oxide HfOx with a thickness of about 40 nm were obtained by electron beam sputtering at di erent oxygen ow rates in the chamber. The electrophysical properties of lms in air and vacuum were studied. It is shown that the temperature dependences of lm conductivity, measured in vacuum inthe temperature range from 20 to 180 ◦C, have an activation character with an activation energy of 0.82 ±0.02 eV. It has been suggested that charge transfer in the resulting lms is determined by the activation of electrons into the conduction band from the donor level associated with oxygen vacancies. It was found that the conductivity of lms in air changes greatly with varying oxygen ow, while in vacuum the conductivity is practically independent of the oxygen ow. This indicates signi cant di erences in the surface properties of lms obtained at di erent oxygen ows in the chamber during the deposition process.

Effects of Hydrogen Doping on a-GIZO Thin-Film Transistors With Hafnium Dioxide Gate Insulators Formed by Atomic Layer Deposition at Different Temperatures

Effects of Hydrogen Doping on a-GIZO Thin-Film Transistors With Hafnium Dioxide Gate Insulators Formed by Atomic Layer Deposition at Different Temperatures

Random telegraph noise characteristic of nonvolatile resistive random access memories based on optical interference principle

The influence of random telegraph noise (RTN) could reduce the reading margin, which would cause computational errors in data recognition. This paper proposes a current sensor based on the principle of optical fiber interference, which can avoid the interference generated during the RTN testing process and improve the accuracy due to its passive characteristics. In this study, a hafnium oxide based memristor was fabricated, the switching voltages of Cu and TiN as the top electrodes are 0.2 V and 0.15 V, respectively. In addition, the RTN spectral density of the two device structures in LRS increases from 10−5 to 10−1 A2 Hz−1 and from 10−5 to 101 A2 Hz−1 with increasing applied voltage. While the RTN in high resistance state is independent of the applied voltage. Furthermore, based on the analysis of the experimental data, the generation mechanism of the RTN is attributed to local defects and the capture or emission of carriers by traps.

Fast Emitting Nanocomposites for High‐Resolution ToF‐PET Imaging Based on Multicomponent Scintillators

AbstractTime‐of‐Flight Positron Emission Tomography (ToF‐PET) is a medical imaging technique, based on the detection of two back‐to‐back γ‐photons generated from radiotracers injected into the body. Its limit is the ability of employed scintillation detectors to discriminate in time the arrival of γ‐pairs, that is, the coincidence time resolution (CTR). A CTR < 50 ps will enable fast imaging with ultralow radiotracer dose. Monolithic materials do not have simultaneously the required high light output and fast emission characteristics, thus the concept of scintillating heterostructure is proposed, where the device is made of a dense scintillator coupled to a fast‐emitting light material. Here a composite polymeric scintillator loaded with hafnium oxide nanoparticles is presented. This enhanced by +300% its scintillation yield, by surpassing commercial plastic scintillators. The nanocomposite is coupled to bismuth germanate oxide (BGO) realizing a multilayer metascintillator. The energy sharing between its components is observed, which activates the nanocomposite's fast emission enabling a net CTR improvement of 25% with respect to monolithic BGO. These results demonstrate that a controlled loading with dense nanomaterials is an excellent strategy to enhance the performance of polymeric scintillators for their use in advanced radiation detection and imaging technologies.

A nanoscale study of hafnium oxide resistive memory switching dynamics

This paper deals with the set and reset time measurements of a resistive memory consisting of a Ti/TiN/HfO2 layer stack contacted with the tip of a conductive atomic force microscope in ultra high vacuum. We present measurements of the set and reset switching times in voltage pulse regime for different voltages and compliance currents. The experimental results are well reproduced by simulation. We derive analytical expressions for the set and reset times as function of experimental conditions. The effect of voltage and current on reset and set switching times is then discussed with the help of their analytical expressions, which are also applied on standard devices characteristics.

Constructing Deep Traps to Achieve Excellent Dielectric Properties in Crystal-Based HfO2/PEI Nanocomposite Films with Ultralow Filler Loadings.

Mixing fillers featured with wide band gaps in polymers can effectively meet the requirement of higher energy storage densities. However, the fundamental relationship between the crystal structures of fillers and the dielectric properties of the corresponding nanocomposites is still unclear. Accordingly, we introduced ultralow contents of the synthesized cubic Hafnium dioxide (c-HfO2) or monoclinic Hafnium dioxide (m-HfO2) as deep traps into poly(ether imide) (PEI) to explore their effects on dielectric properties and the charge-blocking mechanism. m-HfO2/PEI showed better charge trapping due to the higher electron affinity and deeper trap energy. At room temperature, the 0.4 vol % m-HfO2/PEI maintains an ultralow dielectric loss of 0.008 while obtaining a dielectric constant twice that of pure PEI at 1 kHz, simultaneously outperforming in terms of leakage current density, breakdown strength (452 kV mm-1), discharge energy density (Ud, 5.03 J cm-3), charge-discharge efficiency (η, 92%), and dielectric thermal stability. At 125 °C, it exhibits a considerable Ud of 2.48 J cm-3 and a high η of 85% at 300 kV mm-1, surpassing the properties of pure PEI. This promising work opens up a new path for studying HfO2-derived dielectrics with unique crystal structures.

PROTAC Prodrug-Integrated Nanosensitizer for Potentiating Radiation Therapy of Cancer.

Radiation therapy (RT) is one of the primary options for clinical cancer therapy, in particular advanced head and neck squamous cell carcinoma (HNSCC). Herein, the crucial role of bromodomain-containing protein 4 (BRD4)-RAD51 associated protein 1 (RAD51AP1) axis in sensitizing RT of HNSCC is revealed. A versatile nanosensitizer (RPB7H) is thus innovatively engineered by integrating a PROteolysis TArgeting Chimeras (PROTAC) prodrug (BPA771) and hafnium dioxide (HfO2 ) nanoparticles to downregulate BRD4-RAD51AP1 pathway and sensitize HNSCC tumor to RT. Upon intravenous administration, the RPB7H nanoparticles selectively accumulate at the tumor tissue and internalize into tumor cells by recognizing neuropilin-1 overexpressed in the tumor mass. HfO2 nanoparticles enhance RT effectiveness by amplifying X-ray deposition, intensifying DNA damage, and boosting oxidative stress. Meanwhile, BPA771 can be activated by RT-induced H2 O2 secretion to degrade BRD4 and inactivate RAD51AP1, thus impeding RT-induced DNA damage repair. This versatile nanosensitizer, combined with X-ray irradiation, effectively regresses HNSCC tumor growth in a mouse model. The findings introduce a PROTAC prodrug-based radiosensitization strategy by targeting the BRD4-RAD51AP1 axis, may offer a promising avenue to augment RT and more effective HNSCC therapy.

High-performance MoS2 phototransistors with Hf1–x Al x O back-gate dielectric layer grown by plasma enhanced atomic layer deposition

Molybdenum sulfide (MoS2) as an emerging optoelectronic material, shows great potential for phototransistors owing to its atomic thickness, adjustable band gap, and low cost. However, the phototransistors based on MoS2 have been shown to have some issues such as large gate leakage current, and interfacial scattering, resulting in suboptimal optoelectronic performance. Thus, Al-doped hafnium oxide (Hf1–x Al x ) is proposed to be a dielectric layer of the MoS2-based phototransistor to solve this problem because of the relatively higher crystallization temperature and dielectric constant. Here, a high-performance MoS2 phototransistor with Hf1–x Al x O gate dielectric layer grown by plasma-enhanced atomic layer deposition has been fabricated and studied. The results show that the phototransistor exhibits a high responsivity of 2.2 × 104 A W−1, a large detectivity of 1.7 × 1017 Jones, a great photo-to-dark current ratio of 2.2 × 106%, and a high external quantum efficiency of 4.4 × 106%. The energy band alignment and operating mechanism were further used to clarify the reason for the enhanced MoS2 phototransistor. The suggested MoS2 phototransistors could provide promising strategies in further optoelectronic applications.

Formation mechanism of (Ti, Zr, Hf)C medium-entropy carbide derived from polymer precursors and its modification on the ablative mechanism of C/C-SiC composites

Medium-entropy carbide (MEC) of (Ti, Zr, Hf)C was synthesized and its modification on the ablative mechanism of C/C-SiC composites was investigated. After 60 s oxyacetylene flame test, the mass and linear ablation rates were 1.43 mg/s and 11.1 μm/s, respectively. The evolution of ceramics oxide scale dominated the anti-ablation process, which transfers from (Ti, Zr, Hf)xCyOz, (Ti, Zr, Hf)xSiyOz to (Ti, Zr, Hf)O2, (Zr, Hf)TiO4. With further evaporation of SiO2, the generated (Ti, Zr, Hf)O2 skeleton and the residual liquid oxides ((Zr, Hf)TiO4 and (Zr, Hf)SiO4) can block the oxygen channel and further reduce oxidation of the inner matrix.

Investigation of thermal stress effects during annealing of hafnia-made thin film using molecular dynamics simulations

Hafnia or hafnium oxide is a high-κ dielectric material with paramount importance in the realm of semiconductor devices. Recent advancements in 3D device structures require a few nanometer-thick conformal films on non-planar substrates. During the fabrication stage, the annealing process of thin films has been discovered to mitigate delamination issues at the film-substrate interface. However, it has been observed that the residual stress, which emerges as the film cools to room temperature, may lead to delamination. In this study, we propose an idealized atomistic model to mimic the critical region of a 3D-NAND structure, to get insights into the effect of thermal stress and delamination during the annealing of hafnia-made thin film. We employ molecular dynamics simulation using charge-optimized many-body potential (COMB) to perform heating and cooling simulations for different thicknesses of the hafnia layer. Our results suggest that, during heating, as the annealing temperature increases, the severity of delamination decreases. At extremely low thickness of the hafnia layer, delamination does not occur. However, significant delamination is observed during the cooling process, especially when the high temperature gradient is high.

Hollow Hafnium Oxide (HfO2) Fibers: Using an Effective Combination of Sol-Gel, Electrospinning, and Thermal Degradation Pathway.

In recent years, hafnium oxide (HfO2) has gained increasing interest because of its high dielectric constant, excellent thermal stability, and high band gap. Although HfO2 bulk and film materials have been prepared and well-studied, HfO2 fibers, especially hollow fibers, have been less investigated. In this study, we present a facile preparation method for HfO2 hollow fibers through a unique integration of the sol-gel process and electrospinning technique. Initially, polystyrene (PS) fibers are fabricated by using electrospinning, followed by dipping in a HfO2 precursor solution, resulting in HfO2-coated PS fibers. Subsequent thermal treatment at 800 °C ensures the selective pyrolysis of the PS fibers and complete condensation of the HfO2 precursors, forming HfO2 hollow fibers. Scanning electron microscopy (SEM) characterizations reveal HfO2 hollow fibers with rough surfaces and diminished diameters, a transformation attributed to the removal of the PS fibers and the condensation of the HfO2 precursors. Our study also delves into the influence of precursor solution molar ratios, showcasing the ability to achieve smaller HfO2 fiber diameters with reduced precursor quantities. Validation of the material composition is achieved through thermogravimetric analysis (TGA) and energy-dispersive spectroscopy (EDS) mapping. Additionally, X-ray diffraction (XRD) analysis provides insights into the crystallinity of the HfO2 hollow fibers, highlighting a higher crystallinity in fibers annealed at 800 °C compared with those treated at 400 °C. Notably, the HfO2 hollow fibers demonstrate a water contact angle (WCA) of 38.70 ± 5.24°, underscoring the transformation from hydrophobic to hydrophilic properties after the removal of the PS fibers. Looking forward, this work paves the way for extensive research on the surface properties and potential applications of HfO2 hollow fibers in areas such as filtration, energy storage, and memory devices.

Synthesis of (TiTaNb)<sub><i>x</i></sub>Hf<sub><i>y</i></sub>Zr<sub><i>z</i></sub>C high-entropy carbides resistant to high thermal oxidation by mechanical alloying and spark plasma sintering

This study presents the synthesis of (TiZrHfTaNb)C, (TiTaNb)0.45Hf0.275Zr0.275С and (TiTaNb)0.3Hf0.35Zr0.35С single-phase, high-entropy carbides through mechanical alloying and plasma sintering. High-entropy carbides hold promise for applications in jet engine components. We identified optimal mechanical alloying conditions to achieve powder homogeneity and minimize iron fouling. The microstructure, phase, and chemical compositions of the samples were investigated. At 1600 °C, a sample with a face-centered cubic (FCC) lattice and low content of zirconium and hafnium oxides was formed. Elevating the sintering temperature to 2000 °C facilitated oxide dissolution and the formation of single-phase, high-entropy carbides. The microhardness of the samples ranged from 1600 to 2000 HV, while the compressive strength varied between 600 and 800 MPa. Plasma heating tests demonstrated excellent resistance to thermal oxidation for (TiTaNb)0.3Hf0.35Zr0.35С, withstanding temperatures up to 2250 °C.

Experiences from the cutting of metallic blocks from simulant Fukushima Daiichi fuel debris

ABSTRACT CEA has manufactured a series of Fukushima Daiichi fuel debris simulants, either with depleted uranium oxide or with hafnium oxide as a surrogate of UO2. In ex-vessel compositions resulting from an interaction between corium and concrete, the oxidic phase density becomes lighter than that of the metallic phase, which segregates at the bottom. Three of these metallic phases have been mechanically cut at CEA Cadarache with handsaw and with core boring tool in FUJISAN facility. It appeared that two of these metallic blocks were extremely hard to cut (one from a fabrication with uranium oxide, the other from a simulant block) while the last one was more easily cut. The similarities and differences in metallographic analyses (SEM-EDS and XRD) of these three metal blocks will be presented and discussed. This experience provides useful learnings in view of the cutting and retrieval of fuel debris from Fukushima Daiichi.

Superflexible and Stretchable Ferroelectric Memory on a Biocompatible Platform

AbstractNext‐generation flexible electronics for healthcare applications require biocompatible flexible non‐volatile memory for data storage. Ultra‐thin ferroelectric hafnium oxide films offer great potential for flexible memories due to their potential flexibility and perfect compatibility with modern technologies. This study presents ultra‐flexible and stretchable memory devices based on 10‐nm‐thick Hf0.5Zr0.5O2 film fabricated by an innovative technology involving encapsulation of the devices in a biocompatible organic package. They exhibit high memory functionality (remanent polarization of 27 µC cm−2) and withstand extreme mechanical conditions, including folding in half, multiple bending up to 150 000 bending cycles as well as tension with loads up to 1.5 kg. Further, flexible devices are employed as a platform to elucidate the fundamental role of mechanical stress in ferroelectricity of hafnia both experimentally and theoretically. Direct in situ experiment demonstrates that in‐plane tension causes changes in spontaneous polarization, coercive voltage, permittivity, and conductivity. First‐principle calculations explain the role of mechanical stress in ferroelectric and dielectric properties of hafnia. In applications, this work establishes a foundation for the implementation of biocompatible, high‐performance flexible ferroelectric memory, and in the field of ferroelectric materials fundamentals, it provides insight into the critical role of the residual mechanical stress that is inevitably present in thin films.

Enhancing SiGeSn nanocrystals SWIR photosensing by high passivation in nanocrystalline HfO2 matrix

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 β-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.

Synaptic and resistive switching behaviors of Sm‐doped HfO2 films for bio‐inspired neuromorphic calculations

AbstractArtificial neural network‐based computing is anticipated to surpass the von Neumann bottleneck of traditional computers, thus dramatically boosting computational efficiency and showing a wide range of promising applications. In this paper, sol−gel deposition was used to prepare thin films of samarium‐doped hafnium dioxide (Sm:HfO2). When Sm is doped at a concentration of 4%, it mimics biological synapses; meantime, by voltage scanning, an obvious mimicry of resistive switching can be detected, demonstrating that the technology may be applied to simulate biological synapse characteristics, including long‐term potentiation (depression), short‐term potentiation (depression), paired‐pulse facilitation, and learning rules of spike‐time‐dependent plasticity. Additionally, a pulsed neural network is built on the MNIST dataset to test the memristor's capacity to handle visual input. The findings show the possibility of synthetic synapses in artificial intelligence systems that integrate neuromorphic computing with synaptic brain activity.

Equilibrium Composition of Products in a Hafnium Dioxide–Calcium–Nitrogen–Carbon Mixture at Adiabatic Combustion Temperature

Equilibrium Composition of Products in a Hafnium Dioxide–Calcium–Nitrogen–Carbon Mixture at Adiabatic Combustion Temperature