Amorphous Oxide Research Articles

A restricted dynamic surface self-reconstruction toward high-performance of direct seawater oxidation

The development of highly efficient electrocatalysts for direct seawater splitting with bifunctionality for inhibiting anodic oxidation reconstruction and selective oxygen evolution reactions is a major challenge. Herein, we report a direct seawater oxidation electrocatalyst that achieves long-term stability for more than 1000 h at 600 mA/cm2@η600 and high selectivity (Faraday efficiency of 100%). This catalyst revolves an amorphous molybdenum oxide layer constructed on the beaded-like cobalt oxide interface by atomic layer deposition technology. As demonstrated, a new restricted dynamic surface self-reconstruction mechanism is induced by the formation a stable reconstructed Co-Mo double hydroxide phase interface layer. The device assembled into a two-electrode flow cell for direct overall seawater electrolysis maintained at 1 A/cm2@1.93 V for 500 h with Faraday efficiency higher than 95%. Hydrogen generation rate reaches 419.4 mL/cm2/h, and the power consumption (4.62 KWh/m3 H2) is lower than that of pure water (5.0 KWh/m3 H2) at industrial current density.

Variability and high temperature reliability of graphene field-effect transistors with thin epitaxial CaF2 insulators

Graphene is a promising material for applications as a channel in graphene field-effect transistors (GFETs) which may be used as a building block for optoelectronics, high-frequency devices and sensors. However, these devices require gate insulators which ideally should form atomically flat interfaces with graphene and at the same time contain small densities of traps to maintain high device stability. Previously used amorphous oxides, such as SiO2 and Al2O3, however, typically suffer from oxide dangling bonds at the interface, high surface roughness and numerous border oxide traps. In order to address these challenges, here we use 2 nm thick epitaxial CaF2 as a gate insulator in GFETs. By analyzing device-to-device variability for about 200 devices fabricated in two batches, we find that tens of them show similar gate transfer characteristics. Our statistical analysis of the hysteresis up to 175oC has revealed that while an ambient-sensitive counterclockwise hysteresis can be present in some devices, the dominant mechanism is thermally activated charge trapping by border defects in CaF2 which results in the conventional clockwise hysteresis. We demonstrate that both the hysteresis and bias-temperature instabilities in our GFETs with CaF2 are comparable to similar devices with SiO2 and Al2O3. In particular, we achieve a small hysteresis below 0.01 V for equivalent oxide thickness (EOT) of about 1 nm at the electric fields up to 15 MV cm−1 and sweep times in the kilosecond range. Thus, our results demonstrate that crystalline CaF2 is a promising insulator for highly-stable GFETs.

Engineering the Coordination Environment of Ir Single Atoms with Surface Titanium Oxide Amorphization for Superior Chlorine Evolution Reaction.

The chlorine evolution reaction (CER) is essential for industrial Cl2 production but strongly relies on the use of dimensionally stable anode (DSA) with high-amount precious Ru/Ir oxide on a Ti substrate. For the purpose of sustainable development, precious metal decrement and performance improvement are highly desirable for the development of CER anodes. Herein, we demonstrate that surface titanium oxide amorphization is crucial to regulate the coordination environment of stabilized Ir single atoms for efficient and durable chlorine evolution of Ti monolithic anodes. Experimental and theoretical results revealed the formation of four-coordinated Ir1O4 and six-coordinated Ir1O6 sites on amorphous and crystalline titanium oxides, respectively. Interestingly, the Ir1O4 sites exhibited a superior CER performance, with a mass activity about 10 and 500 times those of the Ir1O6 counterpart and DSA, respectively. Moreover, the Ir1O4 anode displayed excellent durability for 200 h, far longer than that of its Ir1O6 counterpart (2 h). Mechanism studies showed that the unsaturated Ir in Ir1O4 was the active center for chlorine evolution, which was changed to the top-coordinated O in Ir1O6. This change of active sites greatly affected the adsorption energy of Cl species, thus accounting for their different CER activity. More importantly, the amorphous structure and restrained water dissociation of Ir1O4 synergistically prevent oxygen permeation across the Ti substrate, contributing to its long-term CER stability. This study sheds light on the importance of single-atom coordination structures in the reactivity of catalysts and offers a facile strategy to prepare highly active single-atom CER anodes via surface titanium oxide amorphization.

Iron-modified biochar inhibiting Cd uptake in rice by Cd co-deposition with Fe oxides in the rice rhizosphere.

Fe-enriched biochar has proven to be effective in reducing Cd uptake in rice plants by enhancing iron plaque formation. However, the effect of Fe on biochar, especially the biochar with high S content, for Cd immobilization in rice rhizosphere was not fully understood. To obtain eco-friendly Fe-loaded biochar at a low cost, garlic straw, bean straw, and rape straw were chosen as the feedstocks for Fe-enhanced biochar production by co-pyrolysis with Fe2O3. The resulting biochars and Fe-loaded biochars were GBC, BBC, BRE, GBC-Fe, BBC-Fe, and BRE-Fe, respectively. XRD and FTIR analyses showed that Fe was successfully loaded onto the biochar. The pristine and Fe-containing biochars were applied at rates of 0% (BC0) and 0.1% in pot experiments. Results suggested that BBC-Fe caused the highest reduction in Cd content of rice grain, and the reductions were 67.9% and 31.4%, compared with BC0 and BBC, respectively. Compared to BBC, BBC-Fe effectively reduced Cd uptake in rice roots by 47.5%. The exchangeable and acid-soluble fraction of Cd (F1-Cd) in soil with BBC-Fe treatment was 37.6% and 63.7% lower than that of BC0 and BBC, respectively. Compared to BC0, soil pH was increased by 0.53 units with BBC-Fe treatment. BBC-Fe significantly increased Fe oxides (free Fe oxides, amorphous Fe oxides, and complex Fe oxides) content in the soil as well. DGT study demonstrated that BBC-Fe could enhance the mobility of sulfate in the rhizosphere, which might be beneficial for Cd fixation in the rhizosphere. Moreover, BBC-Fe increased the relative abundance of Bacteroidota, Firmicutes, and Clostridia, which might be beneficial for Cd immobilization in the rhizosphere. This work highlights the synergistic effect of loaded Fe and biochar on Cd immobilization by enhancing Cd deposited with Fe oxides.

C-Axis Aligned Composite InZnO via Thermal Atomic Layer Deposition for 3D Nanostructured Semiconductor.

Amorphous oxide semiconductors have been widely studied for various applications, including thin-film transistors (TFTs) for display backplanes and semiconductor memories. However, the inherent instability, limited mobility, and complexity of multicomponent oxide semiconductors for achieving high aspect ratios and conformality of cation distribution remain challenging. Indium-zinc oxide (IZO), known for its high mobility, also faces obstacles in instability resulting from high carrier doping density and low ionization energy. To address these issues and attain a balance between mobility and stability, adopting a highly aligned structure such as a c-axis aligned crystalline IGZO could be advantageous. However, limited studies have reported enhanced electrical performance using crystalline IZO, likely attributed to the high thermal stability of the individual components (In2O3 and ZnO). Here, we first propose a c-axis aligned composite (CAAC) IZO with superior TFT properties, including a remarkable performance of field-effect mobility (μFE) of 55.8 cm2/(V s) and positive-bias-temperature-stress stability of +0.16 V (2 MV/cm, 60 °C, 1 h), as well as a low subthreshold swing of 0.18 V/decade and hysteresis as 0.01 V, which could be obtained through optimization of growth temperature and composition using thermal atomic layer deposition. These results surpass those of TFTs based on nanocrystalline/polycrystalline/amorphous-IZO. We conducted a thorough investigation of CAAC-IZO and revealed that the growth temperature and cation distribution profoundly influence the crystal structure and device properties. Finally, we observed excellent compositional conformality and 97% step coverage of IZO on a high-aspect-ratio (HAR) structure with an aspect ratio reaching 40:1, which is highly promising for future applications. Our results include a detailed investigation of the influence of the crystal structure of IZO on the film and TFT performance and suggest an approach for future applications.

High-performance a-Ga2O3 solar-blind photodetectors by pulsed magnetron sputtering deposition

Solar-blind photodetectors (SBPDs) based on the ultrawide-bandgap semiconductor Ga2O3 have gained attention due to their potential applications in both military and civilian domains. As technology advances, photodetectors are being improved to achieve better energy efficiency, smaller size, and better performance. Solar-blind photodetectors based on a metal-semiconductor-metal structure of amorphous gallium oxide (a-Ga2O3) films were fabricated by pulsed magnetron sputtering deposition (PSD). The photodetector based on amorphous gallium oxide has a responsivity of 71.52 A/W, a fast rising and falling response time of less than 200 ms, a photo-to-dark current ratio (PDCR) of 6.52 × 104, and an external quantum efficiency of 34 526.62%. PSD-prepared gallium oxide SBPDs demonstrate a cost-effective room temperature method for growing gallium oxide and show the advantages of growing gallium oxide.

Formation of iron-rich phyllosilicates in the FeO–SiO2–H2O system during hydrothermal synthesis as a function of pH

Abstract The formation of iron-rich phyllosilicates can occur at different natural or engineered settings. In this study, the influence of pH in the hydrothermal synthesis of iron-rich phyllosilicates was investigated in the pH range 8.50–12.10 after the ageing of the precursor. The synthesized samples were characterized by powder X-ray diffraction, Raman and Mössbauer spectroscopies and transmission electron microscopy. Three domains of pH were identified, and these correlated with silica availability and its speciation in the solution. The formation of 1:1-type FeIII/FeII phyllosilicate was observed between pH 9.67 and 10.75. Above pH 10.75, two types of phyllosilicate-like mineral phases were observed. In addition to 1:1-type FeIII/FeII phyllosilicate, 2:1-type FeIII/FeII phyllosilicate was observed. Below pH 9.67, mainly amorphous silica and iron oxides were observed. The findings show that pH governed the crystallinity and nature of the obtained phyllosilicate-like phases.

DUV optoelectronic bionic synapse based on the MOCVD-deposited amorphous gallium oxide film

Optoelectronic bionic synapses, integrating sensing and processing capabilities, help to break through the limitations of von Neumann structure and are promising in smart sensors, AI robots etc. fields. Here, we fabricated a deep ultraviolet (DUV) optoelectronic bionic synapse with an amorphous gallium oxide (a-GaOx) film deposited by metal–organic chemical vapor deposition (MOCVD). DUV illumination pulses could be facilely written into the bionic synapse, and the written information exhibits non-volatility. By manipulating the illumination pulse number, the pulse width, and the pulse power density, the synapse is capable of transitioning from short-term memory (STM) to long-term memory (LTM), effectively emulating the learning-memory behavior of human brains.

Amorphous Vanadium Oxide Supported on Activated Carbon Prepared by Dielectric Barrier Discharge as an Efficient and Stable Catalyst for Hydroxylation of Benzene to Phenol

Amorphous Vanadium Oxide Supported on Activated Carbon Prepared by Dielectric Barrier Discharge as an Efficient and Stable Catalyst for Hydroxylation of Benzene to Phenol

Atomic layer deposition of multicomponent amorphous oxide semiconductors with sequential dosing of metal precursors

Atomic layer deposition (ALD) is a suitable method for depositing amorphous oxide semiconductors (AOSs) because it has the potential for achieving high performance in complex structures owing to its excellent step coverage and atomic-scale controllability. Multicomponent AOSs are typically deposited using the ALD with a super-cycle method. In this study, multicomponent AOSs, i.e., IZO, ITO, and ITZO, were deposited using ALD by employing a sequential dosing of metal precursors. Their compositions were adjusted by varying the dose time of the indium precursor. Subsequently, we applied the IZO, ITO, and ITZO films in thin-film transistors (TFTs), which demonstrated normal transfer characteristics. The TFT containing ITZO with 73.9 at% indium exhibited a turn-on voltage of −1.01 V, subthreshold swing of 0.09 V/dec, and field-effect mobility of 35.9 cm2/(V s).

Nanopatterning of thin amorphous vanadium oxide films by oxidation scanning probe lithography

Oxidation scanning probe lithography is one of the most promising techniques for nanostructuring. Vanadium oxides constitute a class of functionally rich materials that are promising for various practical applications and have unique physical properties. Currently, the formation of nanocrystals and nanostructures with well-defined dimensions is a challenging task. This study presents a detailed investigation of the processes involved in oxidation scanning probe lithography on the surface of thin amorphous vanadium oxide (VOx) films. It was shown that the oxidizable regions of the film transform into a water-soluble vanadium pentoxide (V2O5) in accordance with classical redox reactions. The oxidation kinetics was shown to be consistent with the Cabrera-Mott model. Dissolving the oxidized regions in water resulted in the formation of nanohole arrays with defined sizes in VOx films. Nanostructures with a depth of less than 0.3 nm and lateral dimensions of less than 50 nm were obtained at relative humidity of about 10 %. It was demonstrated that VOx films about 10 nm thick can be completely oxidized in local areas, enabling the formation of isolated nanostructures. The considered method of nanostructuring VOx is promising for the formation of novel photonic and nanoelectronic devices.

The alternation of flood and ebb tide induced arsenic release and migration from coastal tidal flat sediments in Yellow Sea wetlands: An ex-situ study

Periodic floods and ebb tides driven by seawater affect arsenic (As) behavior in coastal wetlands, which is not fully understood. In this study, we combined DGT, high-throughput sequencing, and real-time quantitative polymerase chain reaction (qPCR) techniques for the first time to investigate the effects of flood and ebb tide on As transformation and mobility in a typical coastal tidal flat wetland by laboratory experiments. In the flood-tide stage, more As was released into the water solution, and As(III) concentration in water solution was notably higher (51 μg/L) than in the ebb-tide stage, especially in SA (sodium acetate addition) treatment. As-methylation also occurred in this stage. The release of As was attributed to the reductive dissolution of amorphous and crystalline Fe oxides bound As induced by microbes. Fusibacter, Sva1033, Bradyrhizobium, Ralstonia, and Desulfobacter were primarily involved in the reduction of As, Fe, and S. The copy numbers of arsC were 20–148 times higher than arrA, suggesting that the detoxification reduction pathway was the primary mechanism of direct As-reduction in the flood-tide stage. However, 2-D high-resolution DGT techniques revealed that the concentrations of As(III) and total As in pore water of sediments in the ebb-tide stage were higher than those in the flood-tide stage. The detected aioA gene indicated that As was oxidized in the sediment surface, resulting in As stabilization by crystalline iron minerals, whereas more As(III) were accumulated in pore water. The reduction pathway mediated by arrA may play a prominent role in the ebb-tide stage. This study provides new insights into As release processes in coastal wetlands in seawater environments, which further deepens our understanding of As biogeochemical cycling behavior in different natural environments.

Strengthening Multi-Factor Authentication Through Physically Unclonable Functions in PVDF-HFP-Phase-Dependent a-IGZO Thin-Film Transistors.

For enhanced security in hardware-based security devices, it is essential to extract various independent characteristics from a single device to generate multiple keys based on specific values. Additionally, the secure destruction of authentication information is crucial for the integrity of the data. Doped amorphous indium gallium zinc oxide (a-IGZO) thin-film transistors (TFTs) using poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) induce a dipole doping effect through a phase-transition process, creating physically unclonable function (PUF) devices for secure user information protection. The PUF security key, generated at VGS = 20V in a 20×10 grid, demonstrates uniformity of 42% and inter-Hamming distance (inter-HD) of 49.79% in the β-phase of PVDF-HFP. However, in the γ-phase, the uniformity drops to 22.5%, and inter-HD decreases to 35.74%, indicating potential security key destruction during the phase transition. To enhance security, a multi-factor authentication (MFA) system is integrated, utilizing five security keys extracted from various TFT parameters. The security keys from turn-on voltage (VON), VGS = 20V, VGS = 30V, mobility, and threshold voltage (Vth) exhibit near-ideal uniformities and inter-HDs, with the highest values of 58% and 51.68%, respectively. The dual security system, combining phase transition and MFA, establishes a robust protection mechanism for privacy-sensitive user information.

Effect of acid catalysts on amorphous graphene oxide aerogel production

AbstractThe acids utilized in the production of graphene oxide aerogel underwent testing, revealing variations from the ones documented in the literature. The powder samples were produced by drying under ambient conditions. They were characterized, and the effect of the graphene oxide aerogels produced using these different acids on sound insulation was investigated. All reaction steps were the same in the study, except that different acids were added in the same molar amounts. Measurements were performed at 200 Hz–6000 Hz frequencies for sound absorption. Samples for sound absorption were prepared in 0.1 mm thickness. According to the results, the aerogel produced with acetic acid provided the best sound insulation at approximately 2000 Hz. We also attempted to explain how these acids affect sound insulation.

Effect of sputtering working pressure on the reliability and performance of amorphous indium gallium zinc oxide thin film transistors

In this study, the reliability and electrical properties of indium gallium zinc oxide (IGZO) thin film transistors (TFTs) are investigated when the working pressure of the sputtering system is varied. As IGZO is deposited at a low working pressure, the sputtering yield increases and the film density increases from 5.84 to 6.00 g/cm3 based on x-ray reflectivity measurements. IGZO TFT sputtered at low working pressure has a mobility of 8.05 cm2/V s, a threshold voltage of 1.25 V, and a subthreshold swing of 0.25 V/dec. In addition, x-ray photoelectron spectroscopy analysis shows that the oxygen content in the film decreases when IGZO is deposited at a low working pressure, resulting in improved positive bias stress reliability due to the oxygen-poor film. Furthermore, the IGZO film deposited at a low working pressure effectively prevents the formation of defects caused by the environment such as H2O molecules.

Fault-tolerant structures against breakdown in heterogeneous ferroelectric PbZr0.52Ti0.48O3 thin films based on adaptive self-repairing effects

The design of fault-tolerant structures against the breakdown of heterogeneous ferroelectric films is essential to enhance the breakdown strength. Based on the self-repairing theory, heterogeneous ferroelectric PbZr0.52Ti0.48O3 (PZT) film capacitors with a fault-tolerant structures against breakdown were synthesized by utilizing dielectric/electrolytic dual characteristics of the amorphous aluminum oxide film (AmAO). The PZT/AmAO composite films with Au top electrodes exhibited significant weak breakdown at low voltages, whereas the breakdown in the composite films with Al top electrodes have been repaired and no longer occurred. Compared to PZT(100 nm)/AmAO(120 nm) composite films with Au top electrodes, breakdown strength of PZT(100 nm)/AmAO(120 nm) composite films with Al top electrodes improves from 278 MV/m to 477 MV/m, energy storage density increased from 14.3 J/cm3 to 22.5 J/cm3, since the heterogeneous interface and structural defects have been repaired by adaptive anodizing of Al electrode under high electric field. Cross-sectional SEM images have confirmed the formation of fresh aluminium oxide films (AAO) at the interfaces of AmAO/Al and PZT/AmAO during the application of an electric field. Defects have been effectively repaired, resulting in an increase in breakdown strength. This study establishes a theoretical and technical foundation for the design of fault-tolerant structures against breakdown in heterogeneous ferroelectric films.

Effects of flooding and warming on soil nitrogen fraction transformation under low‐molecular‐weight organic acid inputs

AbstractFlooding and climate warming lead to the increase of low‐molecular‐weight organic acid (LMWOA) inputs to soil. However, it is unclear what the effects of flooding and climate warming on soil nitrogen fraction transformation under LMWOA input are. Fluvisol was collected in the riparian zone of the Three Gorges Reservoir to conduct an incubation experiment with the treatments of three LMWOAs at five contents, two hydrological environments and two temperatures. Compared with LMWOA input of 0 mg kg−1, the soil nitrogen in ion exchangeable fraction (IEF‐N), strong oxidant extractable fraction (SOEF‐N) and non‐transformable nitrogen (NTF‐N) were increased by 35.77, 54.71 and 25.49 mg kg−1, respectively, under LMWOA input of 40 mmol kg−1. Soil nitrogen in the weak acid extractable fraction (WAEF‐N) was decreased by 117.41 mg kg−1. Microbial biomass nitrogen (MBN) was increased by 25.29 mg kg−1, and calcium carbonate (CaCO3) was decreased by 8.03 g kg−1. The contents of IEF‐N, NTF‐N and amorphous iron oxides were higher under the flooding environment than under the drying environment. In contrast, opposite results were observed for soil nitrogen in the strong alkali extractable fraction (SAEF‐N), SOEF‐N and MBN. IEF‐N and NTF‐N contents were higher at 20°C than at 30°C, and the contents of SOEF‐N and MBN were higher at 30°C than at 20°C. WAEF‐N was dissolved by LMWOA through CaCO3 dissolution. The dissolved WAEF‐N was partly transformed into SOEF‐N and NTF‐N by microbial assimilation and humification. Flooding desorbed SAEF‐N through the crystalline transformation of iron oxides. Flooding inhibited the transformation of IEF‐N to SOEF‐N and promoted the formation of NTF‐N, while warming did the opposite. The results provide a perspective of the bound state between soil and nitrogen for understanding the soil nitrogen cycling and help to assess the impacts of climate warming and flooding on soil nitrogen loss from soil to the surrounding water.

High-mobility wide bandgap amorphous gallium oxide thin-film transistors for NMOS inverters

Wide bandgap gallium oxide thin-film transistor (TFT) is promising for next-generation sustainable energy-efficient power electronics. In particular, amorphous oxide channel exhibits inherent advantages on mass productions based on a low-temperature processability compatible with cost-effective large-sized glass. Here, we developed hydrogen defect termination to produce amorphous-GaOx (a-GaOx) channel for n-channel oxide-TFT and demonstrated high-mobility a-GaOx-TFT exhibiting a high saturation mobility (μsat) of ∼31 cm2 V−1 s−1, threshold voltage (Vth) of ∼3.3 V, a current on/off ratio of ∼108, and subthreshold swing value (s-value) of ∼1.17 V·dec−1. The study found that oxygen conditions during the channel fabrication process, i.e., oxygen partial pressure during the film deposition and post-thermal annealing atmospheres, were critical for the TFT performances of gallium oxide-TFTs, and subgap defects originated from low-valence Ga+ state and excess oxygen rather than oxygen vacancy had a large responsibility for the device performances. The finding explains why the development of gallium oxide-TFTs is largely behind the other oxide-TFTs. We also fabricated depletion and enhancement-mode a-GaOx-TFTs and developed a full-swing zero-VGS-load inverter with high voltage gain ∼200 and sufficient noise margins. The present study demonstrates a high potential of gallium oxide channel for low-temperature processed n-channel oxide-TFT for next-generation electronic applications.

Surface Reconstruction on Metal Nitride during Photo-oxidation.

The efficient conversion and storage of solar energy for chemical fuel production presents a challenge in sustainable energy technologies. Metal nitrides (MNs) possess unique structures that make them multi-functional catalysts for water splitting. However, the thermodynamic instability of MNs often results in the formation of surface oxide layers and ambiguous reaction mechanisms. Herein, we present on the photo-induced reconstruction of a Mo-rich@Co-rich bi-layer on ternary cobalt-molybdenum nitride (Co3 Mo3 N) surfaces, resulting in improved effectiveness for solar water splitting. During a photo-oxidation process, the uniform initial surface oxide layer is reconstructed into an amorphous Co-rich oxide surface layer and a subsurface Mo-N layer. The Co-rich outer layer provides active sites for photocatalytic oxygen evolution reaction (POER), while the Mo-rich sublayer promotes charge transfer and enhances the oxidation resistance of Co3 Mo3 N. Additionally, the surface reconstruction yields a shortened Co-Mo bond length, weakening the adsorption of hydrogen and resulting in improved performance for both photocatalytic hydrogen evolution reaction (PHER) and POER. This work provides insight into the surface structure-to-activity relationships of MNs in solar energy conversion, and is expected to have significant implications for the design of metal nitride-based catalysts in sustainable energy technologies.

Stable and low loss oxide layer on α-Ta (110) film for superconducting qubits

The presence of amorphous oxide layers can significantly affect the coherent time of superconducting qubits due to their high dielectric loss. Typically, the surface oxides of superconductor films exhibit lossy and unstable behavior when exposed to air. To increase the coherence time, it is essential for qubits to have stable and low dielectric loss oxides, either as barrier or passivation layers. In this study, we highlight the robust and stable nature of an amorphous tantalum oxide layer formed on α-Ta (110) film by employing chemical and structural analyses. Such kind of oxide layer forms in a self-limiting process on the surface of α-Ta (110) film in piranha solution, yielding stable thickness and steady chemical composition. Quarter-wavelength coplanar waveguide resonators are made to study the loss of this oxide. One resonator has a Qi of 3.0 × 106 in the single photon region. The Qi of most devices are higher than 2.0 × 106. Moreover, most of them are still over 1 × 106 even after exposed to air for months. Based on these findings, we propose an all-tantalum superconducting qubit utilizing such oxide as passivation layers, which possess low dielectric loss and improved stability.