Doped Hafnium Research Articles

Solid-State Lithium-Ion Superionic Electrolytes with Reduced Moisture Sensitivity

The remarkable safety and high energy density of solid-state batteries (SSBs) created significant advantages in the development of next-generation energy storage. The properties of these batteries are highly dependent on the characteristics of solid-state electrolytes (SSEs), making them a crucial material in the development of such batteries. Following diverse principles of material design, lithium halide SSEs, particularly Li3InCl6, open new opportunities in the development of SSBs due to their unique properties including broad electrochemical stability window, high lithium-ion conductivity, and excellent deformability. Through a mechano-thermal synthesis approach, Li3InCl6 demonstrates substantial ionic conductivity at room temperature. We studied the temperature-dependent behavior of Li3InCl6 by using in-situ/operando techniques such as XRD and XPS. However, its susceptibility to moisture poses a significant challenge for practical implementation in SSBs. To overcome this limitation, this research is focused on a novel solution: hafnium doping of Li3InCl6. Integrating hafnium into the Li3InCl6 structure results in a substantial improvement in electrochemical performance. The Li2.6In0.6Hf0.4Cl6 solid-state electrolyte not only showcases heightened ionic conductivity but also demonstrates improved resistance to moisture. The achieved ionic conductivity reaches approximately 1 mS cm-1, marking a significant 3.5-fold increase compared to Li3InCl6. Noteworthy is the fact that, after 5 hours of exposure to air with 15% humidity, the observed reduction in ionic conductivity for Li2.6In0.6Hf0.4Cl6 is 37%, a notably lower decrease compared to the 57% reduction seen in Li3InCl6.The efficacy of hafnium doping provides a crucial advancement in the field of solid-state electrolytes, promising a transformative impact on next-generation energy storage systems.

Distinguishing the Rhombohedral Phase from Orthorhombic Phases in Epitaxial Doped HfO2 Ferroelectric Films.

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.

Understanding and tuning negative longitudinal piezoelectricity in hafnia

Most piezoelectric materials exhibit a positive longitudinal piezoelectric effect (PLPE), while a negative longitudinal piezoelectric effect (NLPE) is rarely reported or paid much attention. Here, utilizing first-principles calculations, we unveil the origin of negative longitudinal piezoelectricity in ferroelectric hafnia by introducing the concept of weighted projected bond strength around cation in the c direction (WPBc), which is proposed to quantitatively characterize the asymmetric bonding stiffness along the strain direction. When the WPBc is anti-parallel to the direction of bulk spontaneous polarization, the polarization decreases with respect to tensile strain and leads to a negative piezoelectricity. Furthermore, to confirm the influence of WPBc on the piezoelectric effect and understand how the value of WPBc influences the piezoelectric coefficient e33, we acquire both the piezoelectric coefficient of doped hafnia and the corresponding bonding environment around each cation. The finding reveals that the more negative piezoelectric coefficient can be achieved through a concurrent achievement of the more negative average WPBc and the lower standard deviation (STD) of WPBc. In addition, the Sn-doped hafnia with the lowest average WPBc and smaller STD-WPBc is identified to have the highest piezoelectric coefficient (−2.04 C/m2) compared to other dopants, showing great potential in next-generation electromechanical devices.

Nanoscale-doped dual-channel for improved performance and reliability of Hf: IGTO / a-IGTO thin film transistor

Amorphous oxide semiconductors are widely used in the backplane thin film transistors (TFTs) of displays and are extensively researched as materials for next-generation memory devices. However, they face reliability degradation due to stress factors such as thermal, bias, and light exposure. To mitigate these issues, extensive research is focused on improvements, including doping, enhancing crystallinity, and applying pre-and post-treatments. This study investigates the significantly improved reliability and electrical properties of amorphous indium gallium tin oxide (a-IGTO) TFTs by adopting a dual-channel configuration through simultaneous co-sputtering of HfO2 and IGTO targets. The device fabrication involved co-sputtering HfO2 and IGTO at the gate oxide interface, followed by depositing an IGTO-only layer, rather than doping the entire channel material. The effect of varying Hf concentration was evaluated by applying different HfO2 sputtering powers. Optimal hafnium doping reduced the threshold voltage of the a-IGTO TFT from −0.85V to 0.15V compared to the pristine a-IGTO TFT, while enhancing the field-effect mobility (μFE). Furthermore, the Hf-doped device exhibited improved stability, with a reduced threshold voltage shift (ΔVth) under positive (+15 V) and negative(-15 V) bias stress at 3000s, decreasing from 11.5 V to 4.8 V, and 4.7 V–1.1 V, respectively. This study proposes a novel device fabrication method to enhance the reliability of amorphous oxide semiconductor, addressing their inherent stress-related issues.

Influence of Hf doping on structural, morphological, optical and electrochemical properties of NiO thin films: Electrochromic application

In this study, the authors investigated the influence of hafnium doping on the properties of NiO thin films using the spray pyrolysis (SP) method. A comprehensive analysis was conducted to evaluate the structural, morphological, optical, and electrochemical characteristics of the deposited films. Techniques such as X-ray diffraction analysis (XRD), Raman spectroscopy, scanning electron microscopy (FESEM), energy dispersive analysis by X-ray (EDS), UV–Vis–NIR spectrophotometry, cyclic voltammetry (CV), and chronoamperometry (CA) were employed. XRD examination revealed that the NiO thin films exhibit a polycrystalline cubic phase, with a preferred orientation along the (111) plane. The successful integration of Hf ions into the NiO matrix was confirmed by the Raman spectrum. SEM images depicted the formation of dense and uniform nanograins on all film surfaces, free from any cracks. EDS analysis and elemental mapping indicated uniform and homogeneous distribution of Ni, O, and Hf elements across the films. The optical analysis suggested a decrease in the optical band gap energy from 3.54 eV to 3.49 eV with an increase in hafnium doping concentration. Electrochemical results revealed a continuous improvement in specific capacitance with Hf doping. The NHf6 sample reached 65 F. g−1 at 5 mV s−1, compared to 46 F. g−1 at 5 mV s−1 for the NHf0 sample. However, the NHf4 film exhibited the highest optical density variation (49%), shortest response times (tb = 3.58 s, tc = 4.67 s), and the largest coloration efficiency (63.39 cm2/C), indicating enhanced electrochromic performance at this Hf doping rate. These findings suggest that Hf-doped NiO holds promise as a candidate for use as a counter-electrode in electrochromic devices.

Programmable Ferroelectricity in Hf0.5Zr0.5O2 Enabled by Oxygen Defect Engineering.

Ferroelectricity, especially the Si-compatible type recently observed in hafnia-based materials, is technologically useful for modern memory and logic applications, but it is challenging to differentiate intrinsic ferroelectric polarization from the polar phase and oxygen vacancy. Here, we report electrically controllable ferroelectricity in a Hf0.5Zr0.5O2-based heterostructure with Sr-doped LaMnO3, a mixed ionic-electronic conductor, as an electrode. Electrically reversible extraction and insertion of an oxygen vacancy into Hf0.5Zr0.5O2 are macroscopically characterized and atomically imaged in situ. Utilizing this reversible process, we achieved multilevel polarization states modulated by the electric field. Our study demonstrates the usefulness of the mixed conductor to repair, create, manipulate, and utilize advanced ferroelectric functionality. Furthermore, the programmed ferroelectric heterostructures with Si-compatible doped hafnia are desirable for the development of future ferroelectric electronics.

Emergent superconductivity in doped ferroelectric hafnia

Emergent superconductivity in doped ferroelectric hafnia

Exploring Hafnium-induced transformations in SnSe allotropes: Insights into structural, electronic, optical, and mechanical modifications for enhanced optoelectronic utilization

In this comprehensive DFT study, we delve into the transformative influence of Hafnium (Hf) doping on the intrinsic properties of α − SnSe, β − SnSe, γ − SnSe, δ − SnSe, and ε − SnSe allotropes. By employing advanced analytical techniques, we elucidate the nuanced structural and electronic modifications, unveiling a potent potential for electronic application optimization. After doping, there's a consistent decrease in work function in all studied variations, suggesting a heightened electron release propensity. This discovery could have meaningful impacts, not only on the fields of electronics but also profoundly on the optoelectronic domain. The spotlight, however, shines intensely on the optical properties. Key parameters—including the dielectric function, absorption coefficient, refractive index, and reflectivity—undergo discernible shifts, especially in the δ-SnSe allotrope, emphasizing a broadened applicability spectrum. This optical versatility paves the way for SnSe's potential in solar cells, LEDs, photodetectors, optical modulators, and beyond. On the mechanical front, elasticity evaluations unearthed patterns of enhanced resilience, with Hf doping imparting increased in-plane stiffness, occasionally at the expense of ductility. In conclusion, our findings champion Hf-doped SnSe structures as promising contenders for groundbreaking optoelectronic devices, setting a foundation for future material innovation and application in contemporary technology.

Influence of niobium and hafnium doping on the wear and corrosion resistance of coatings based on ZrN

The properties of coatings based on the ZrN system with the introduction of hafnium and zirconium (ZrN, (Zr,Nb)N and (Zr,Hf)N), deposited on a Ti6Al–4V titanium alloy substrate are compared. Coatings are deposited by controlled accelerated arc-physical vapor deposition, and the structure of the coatings is studied using a transmission electron microscope. A comparison is made of both the mechanical (hardness, wear resistance, scratch strength) and anticorrosion (in a 3 % solution of NaCl) properties. The (Zr,Hf)N coating (22 at% Hf and 78 at% Zr) has the maximum hardness (HV, 3225 ± 73) and wear resistance. This coating also exhibits higher corrosion resistance. In contrast, introducing Nb into the coating composition reduces the corrosion resistance. This combination of beneficial properties makes the (Zr,Hf)N coating useful for conditions in which the surfaces of parts must simultaneously have high wear resistance, strength, and corrosion resistance.

Ferroelectric and Antiferroelectric Phenomenon in Lanthanum Doped Hafnium Based Thin Films

Ferroelectric and Antiferroelectric Phenomenon in Lanthanum Doped Hafnium Based Thin Films

Three-terminal vertical ferroelectric synaptic barristor enabled by HZO/graphene heterostructure with rebound depolarization

Ferroelectric switching devices employing doped hafnium oxide (HfO2)-based thin films have expanded their range of electronic applications from densely-packed memory to brain-inspired artificial synapses. Here, we introduce a novel and distinctive three-terminal vertical device using a heterogeneous stack of hafnium-zirconium-oxide (HZO) thin film and graphene, called ferroelectric synaptic barristor (FSB), which can function as a scalable artificial synapse for energy-efficient neuromorphic computing. Electrostatic gating in the FSB can simultaneously reorient the polarization degree and the direction of HZO as well as the Schottky barrier and the trapping degree at the graphene interface. With these peculiar controlling factors, this process mimics crucial synaptic characteristics with rebound depolarization (RD), which converts an incoming inhibitory pre-spike into cell excitation. Using the RD function mediated by both ferroelectric switching and trap-mediated charge transport, the FSB exhibited a stable long-term potentiation/depression for 5000 identical pulse schemes with excellent linearity, high yield (47/48 cells), and a good state-retaining ability for 5000 s. The learning ability and energy consumption based on a single neural network were evaluated using MNIST handwritten digits and fashion patterns. The FSB with RD exhibited better accuracy (90.03% and 74.65% for handwritten digits and fashion patterns, respectively), fast and low-power learning ability than that without RD. Our FSB device can bring the advantages of conventional ferroelectric synaptic devices while mitigating their ingrained technical and operational issues.

Comparative study of Negative Capacitance Field Effect Transistors with different doped hafnium oxides

Negative Capacitance Field Effect Transistors are well known for their superior performance over MOSFET and are a viable candidate to succeed the baseline FET in time ahead. We have studied the performance of 32 nm planar MOSFET with doped hafnium dioxide as a ferroelectric material. The functioning of the NCFET is entirely dependent on the equivalence between the ferroelectric and MOS capacitance. Our simulation results clearly indicated that the Sr doped HfO2 has close capacitance matching with MOS capacitance, when compared with other dopant material (Si, Al and Zr). This also reflects in the performance parameters (drain current and transconductance characteristics) of the device designed. Also, we have designed a resistive load inverter with doped hafnium dioxide, Sr doped among them has an edge over the other ferroelectric material in terms of noise margin and static power dissipation.

Indium and hafnium chloride modified titanium oxide thin films

Titanium oxide (TiO2) thin films were prepared by the sol-gel spin-coating technique. The influences of indium (In), hafnium (Hf), and In&Hf doping on electrochemical and structural properties were investigated. The structural properties of undoped and doped TiO2 were investigated using thermogravimetric/differential thermal (TG/DTA), X-ray Powder Diffraction (XRD), and atomic force microscopy (AFM). The optical properties were investigated using ultraviolet–visible (UV–Vis) spectroscopy, and band gap energies were calculated using the Tauc method from transmission measurement. The results showed that TiO2 had better electrochemical properties, and the band gap increased with In&Hf doping.

Controlling ferroelectric properties in Y-doped HfO2 thin films by precise introduction of oxygen vacancies

Thin-film ferroelectric doped hafnia has emerged as a promising candidate for non-volatile computer memory devices due to its CMOS compatibility. The ferroelectricity in thin-film HfO2 is defined by the polar orthorhombic phase, whose stabilization depends on various parameters, such as doping species, stress, thickness, crystallization annealing temperature, etc. The concentration of oxygen vacancies is yet another parameter affecting the stabilization of the ferroelectric phase in HfO2 thin films. Here, we report on the effect of oxygen vacancies introduced in Y-doped HfO2 (HYO) films during reactive pulsed laser deposition on their ferroelectric properties, which we systematically study by correlating structural and electrical properties. Among different techniques, near-edge x-ray absorption fine structure analysis is successfully employed to distinguish between structurally similar ferroelectric orthorhombic and paraelectric tetragonal phases. It is shown that oxygen vacancies introduced at a certain concentration in HYO films can be used as a tool to control the phase composition as well as to decrease the formation energy (crystallization temperature) of the ferroelectric phase. Based on these results, we demonstrate a back-end-of-line compatible ferroelectric HYO capacitor device with competitive functional properties.

Dosimetric characterization for optimum concentration in rare earth doped hafnium oxide nanophosphors for medical radiotherapy applications

Rare earth (RE) doped HfO2 NPs was prepared using the co-precipitation method. This study focuses on the dosimetric characteristic of rare earth (Gd3+,Eu3+,Ho3+) activated HfO2 nanoparticles as potential thermoluminescence (TL) dosimeter for radiation therapy dosimetry. The selected dopant concentrations of 2.5 mol% of Gd, 7.5 mol% of Eu and 2.5 mol% of Ho were irradiated with a clinical gamma photon beam. From the study of dosimetric characterization, it is observed that there is an enhancement of dose response by incorporating rare earth materials. The results obtained in this work show that the Eu3+(7.5 mol%) satisfies the dosimetric characteristic (expect fading) other than an optimized dopant concentration of Gd and Ho. Eu3+ showed that the dosimetric features of reproducibility are high, the linear behavior for photon dose is a good and high degree of fading. The fading factors for the proposed dosimeters at room temperature, which explicit the high loss of TL signal is due to the un-stabilization of trapped charged effects. This detailed study can be useful for the further development of highly efficient ionizing radiation dosimetry.

Synergistic effect of hafnium doping in tin diselenide for enhanced photodetection application

For long, photo-sensitive materials of transition metal dichalcogenides (TMDCs) have been explored in the semiconductor industry. TMDCs have superior environmental stability, apart from their strong light-matter interaction. Although Hafnium-based semiconductors capture great interest due to their high carrier mobility at room temperature, their optoelectronic applications are yet to be explored. Herein, we demonstrate the growth of large size HfxSn1-xSe2 (x = 0, 0.05, 0.1, 0.15, 0.2) single crystals by direct vapor transport (DVT) technique and optimized photodetection application. Grown crystals have a highly crystalline nature, attributing to the substitutional doping of Hf4+ on Sn4+-sites. With optimized stoichiometry and improved crystallinity, 5% Hf doped SnSe2 shows the superior photoresponse with the maximum photocurrent 198.28 μA under 120 mW/cm2 blue light intensity. The detector shows photoresponsivity of 16.52 mA/W and specific detectivity 19.44 × 109 Jones owing to the highest crystallite size for 5% HF doped SnSe2. This excellent result shows promising application of HfxSn1-xSe2 (x = 0, 0.05, 0.1, 0.15, 0.2) crystals as high-performance photodetector by improved crystalline nature.

Improved Ferroelectric Properties in Hf0.5Zr0.5O2 Thin Films by Microwave Annealing.

In the doped hafnia(HfO2)-based films, crystallization annealing is indispensable in forming ferroelectric phases. In this paper, we investigate the annealing effects of TiN/Hf0.5Zr0.5O2/TiN metal-ferroelectric-metal (MFM) capacitors by comparing microwave annealing (MWA) and rapid thermal annealing (RTA) at the same wafer temperature of 500 °C. The twofold remanent polarization (2Pr) of the MWA device is 63 µC/cm2, surpassing that of the RTA device (40 µC/cm2). Furthermore, the wake-up effect is substantially inhibited in the MWA device. The orthorhombic crystalline phase is observed in the annealed HZO films in the MWA and RTA devices, with a reduced TiN and HZO interdiffusion in MWA devices. Moreover, the MFM capacitors subjected to MWA treatment exhibit a lower leakage current, indicating a decreased defect density. This investigation shows the potential of MWA for application in ferroelectric technology due to the improvement in remanent polarization, wake-up effect, and leakage current.

Regulating Sn self-doping and boosting solar water splitting performance of hematite nanorod arrays grown on fluorine-doped tin oxide via low-level Hf doping

Hematite (α-Fe2O3) nanorod arrays grown on fluorine-doped tin oxide (FTO) substrate exhibit outstanding solar water splitting efficiency, benefiting from Sn self-doping induced by high-temperature annealing. However, this Sn self-doping couldn’t be freely controlled without changing the optimized annealing conditions, which limits the further improvement of their photoelectrochemical (PEC) properties. Here, we report a facile hydrothermal synthesis with subsequent annealing approach to regulate the Sn diffusion via hafnium (Hf) doping as well as enhance the PEC performance of hematite photoanode. Upon increasing the Hf doping concentration, the Sn self-doping content was continuously suppressed. The very low doping-level of Hf (i.e., atomic Hf/Fe = 0.13 ∼ 1.54%) was sufficient for enhancing the electrical conductivity. The Hf-doped α-Fe2O3 with the optimized dopant concentration (Hf/Fe = 1.34%, denoted as 0.25-Hf-Fe2O3) showed a photocurrent density of 1.79 mA/cm2 at 1.23 V vs. RHE, 70% higher than that of the Sn self-doped one (Pristine-Fe2O3). The donor density of 0.25-Hf-Fe2O3 increased 2.5 times compared to Pristine-Fe2O3 while its space-charge resistance and charge transfer resistance declined by 40% and 22%, respectively, verifying Hf doping improves the charge carrier density and accelerates the charge transfer for solar water oxidation. We offered here a prospective dopant alternative for preparing superior hematite-based photoanode.

Hybrid Deep Learning Crystallographic Mapping of Polymorphic Phases in Polycrystalline Hf0.5 Zr0.5 O2 Thin Films.

By controlling the configuration of polymorphic phases in high-k Hf0.5 Zr0.5 O2 thin films, new functionalities such as persistent ferroelectricity at an extremely small scale can be exploited. To bolster the technological progress and fundamental understanding of phase stabilization (or transition) and switching behavior in the research area, efficient and reliable mapping of the crystal symmetry encompassing the whole scale of thin films is an urgent requisite. Atomic-scale observation with electron microscopy can provide decisive information for discriminating structures with similar symmetries. However, it often demands multiple/multiscale analysis for cross-validation with other techniques, such as X-ray diffraction, due to the limited range of observation. Herein, an efficient and automated methodology for large-scale mapping of the crystal symmetries in polycrystalline Hf0.5 Zr0.5 O2 thin films is developed using scanning probe-based diffraction and a hybrid deep convolutional neural network at a 2 nm2 resolution. The results for the doped hafnia films are fully proven to be compatible with atomic structures revealed by microscopy imaging, not requiring intensive human input for interpretation.

Compositionally graded specimen made by laser additive manufacturing as a high-throughput method to study radiation damages and irradiation-assisted stress corrosion cracking

This study demonstrates the feasibility of using compositionally gradient specimens, fabricated by laser additive manufacturing (AM) and post-AM thermo-mechanical treatment, to accelerate alloy synthesis, radiation experiment, and the assessment of irradiation properties in light water reactor environments. The effects of minor Hafnium (Hf) doping in austenitic 316L stainless steel (SS) was selected as the topic of interest. By comparing to the data in literature, we confirmed that the compositionally graded specimen produces the same trend of void swelling, dislocation loops, radiation-induced segregation (RIS), radiation hardening as the wrought specimen produced by cast/forging process. Hf suppressed most radiation damages through strong interaction with point defects. The work also demonstrates the use of compositionally gradient specimens to study the irradiation-assisted stress corrosion cracking (IASCC) susceptibility of Hf-modified SS. While the suppression of radiation hardening and RIS are consistent with the IASCC mitigation by Hf, we emphasize Hf can alter the intrinsic deformation behavior of 316L SS, which reduces grain-boundary strain localization. The advantages and challenges of using compositionally gradient design for high-throughput nuclear alloy development and qualification are also discussed.