Thin Oxide Research Articles

Fundamental Insights into Copper-Epoxy Interfaces for High-Frequency Chip-to-Chip Interconnects.

Future processes and materials are needed to enable multichip packages with chip-to-chip (C2C) data rates of 50 GB/s or higher. This presents a fundamental challenge because of the skin effect, which exacerbates signal transmission losses at high frequencies. Our results indicate that smooth copper interconnects with relatively thin cuprous oxides (Cu2O, CuI) and amine-functional silane adhesion promoters improve interfacial adhesion with epoxy dielectrics by nearly an order of magnitude. For the first time, we present X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy evidence of Cu(I)-O-Si bond formation at silane-treated interfaces. Thus, relatively smooth interconnects can benefit from reduced skin losses while maintaining their mechanical integrity and reliability. Failure mechanisms of Cu interconnects with cuprous and cupric oxide (CuO, CuII) are explored using scanning electron microscopy (SEM) and Auger electron spectroscopy (AES). These results indicate that both cupric oxides and relatively thick cuprous oxide interfaces lead to relatively weaker interfaces compared with thin cuprous oxides with adhesion promoters.

Effect of Annealing Time on Pitting, Intergranular Corrosion, and Hardness of Stainless Steels

Stainless steels are the material that has chromium as a main component. The chromium content reacts with oxygen in air, subsequently, forms thin chromium oxide film on the surface of stainless steels. Thus, when these steels are exposed to high temperature for a long period of time in many applications, chromium carbide could precipitate along the grain boundary and reduce the corrosion resistance. This project is conducted to study annealing time effect on stainless steels when exposed to high temperature at various exposure time periods. Three different kind of stainless steels, namely, AISI 304, AISI 304D and AISI 2205 were used in this study. Stainless steels were heated at 600°C for 0, 6, 24, 48 and 96 hours, then cool down in air. Consequently, the investigations were performed by using double-loop Electrochemical Potentiokinetic Reactivation (DL-EPR) and Cyclic Potentiodynamic Polarization (CPP) to study degree of sensitization and film properties. In addition, chromic acid and oxalic acid were used as reagent of acid etching to observe microstructures. Finally, Vickers hardness test were also conducted. Percentage degree of sensitization increased from 2.93% to 62.20% in AISI 304, increased from 5.26% to 55.54% in AISI 304D and from 12.19% to 69.35% in AISI 2205. The pitting potential decreased from 0.47 mV to 0.23 mV for AISI 304 but remained relatively constant for AISI 304D and AISI 2205. The results indicated that after the specimens were exposed to high temperature for a long period of time, all specimens had more chromium depleted areas, more carbide along the grain boundaries, worse film quality and small changes in hardness value.

Enhanced microwave absorption properties of Ti3AlC2 particles modified by a facile preoxidation strategy

MAX phases are considered to be promising microwave absorbing materials in fifth-generation (5G) communications, but their high electrical conductivity causes impedance mismatching, weakening their ability to absorb microwaves. Here, we present a universal preoxidation strategy to improve the impedance matching and the microwave absorption performance of a Ti3AlC2 MAX phase absorbing material. The microwave absorption properties of Ti3AlC2 particles were enhanced after preoxidation at temperatures of 500-700 °C for only 30 min in air, as compared with unoxidized Ti3AlC2 particles. More interestingly, the 600 °C-preoxidized Ti3AlC2 material reached a minimum reflection loss (RLmin) value of -50.56 dB at 8.87 GHz, superior to -12.36 dB at 12.82 GHz for the original Ti3AlC2 material. The preoxidized Ti3AlC2 particles were covered by a thin oxidation layer comprising both amorphous TiO2 (a-TiO2) and rutile TiO2 (R-TiO2). The oxidation layer endows the preoxidized Ti3AlC2 particles with good impedance matching, and a large number of nano-interfaces of a-TiO2/R-TiO2 and micro-interfaces of a-TiO2/Ti3AlC2 also contribute to the dielectric loss mechanism, thus improving its microwave absorption ability. This work provides a practical strategy for the fundamental study and the optimal design of MAX microwave absorbing materials.

Enhanced ablation resistance and mechanical behavior of spark plasma sintered ZrB2-SiC composites with TiC addition

The study evaluated the ablation resistance and mechanical behavior of spark plasma sintered ZrB2-25 vol% SiC-TiC (5–15 vol%) composites. The addition of TiC improved ablation resistance by promoting the formation of ZrO2.TiO2 and TiO2 phases on the oxidized composites. The ZrB2-25 vol% SiC-15 vol% TiC composite exhibited the lowest mass ablation rate of 0.11 mg/s and maximum fracture toughness of 5.8±0.29 MPa.m0.5. After ablation, SiC particle pull-out, crack deflection and crack bridging were identified as the primary toughening mechanisms. The maximum microhardness of 23.01±1.18 GPa and compressive strength of 1688.2±75.5 MPa were obtained for the ZrB2-25 vol% SiC-10 vol% TiC composite, which correspond to 92.86 % and 94.31 % of their respective maximum values prior to ablation. Furthermore, nanoindentation studies revealed significant improvements in both elastic modulus and nanohardness with the addition of TiC due to reduction in porosity and refinement in SiC grain size. After ablation, the elastic modulus and nanohardness reduced. However, the ZrB2-25 vol% SiC-10 vol% TiC composite retained a maximum elastic modulus of 433.61 GPa and nano-hardness of 21.88 GPa. The oxidation behavior of ZrB2-SiC composites containing TiC was analyzed at 1500°C for 6 hours in air. The TiC-containing composite exhibited lower mass gain, lower parabolic oxidation rate constant and a thin oxide layer compared to the ZrB2-SiC composites.

Self-assembly fabrication of SASN@GO composites with high electrostatic safety and thermal stability performances

ABSTRACT The high electrostatic discharge (ESD) sensitivity and mechanical sensitivity of silver acetylide-silver nitrate (SASN) seriously affects its application. For solving this problem, novel SASN@GO nanocomposites were successfully prepared by a self-assembly method. Thin sheet graphene oxide (GO) was coated on the surface of SASN, and prevented the agglomeration of SASN nanoparticles effectively. GO content in SASN@GO nanocomposites was controlled (0.5 ~ 1.5 wt%) to balance explosive performance and safety. Results reveal that SASN@(1%)GO exhibits the best thermal safety and desensitization, with thermal decomposition temperature, impact sensitivity (I s), friction sensitivity (F s) and electrostatic energy at 50% ignition probability (E 50) of 208.2°C, 1.96 J, 128 N and 0.64 mJ respectively, which are much better than that of SASN, indicating safety performances of SASN are improved through the introducetion of a small amount of GO. This work provides a strategy for reducing the explosion risk of SASN.

Atomic Layer Deposition for Stable InP-Based On-Chip Quantum Dot microLEDs: Hybrid Quantum Dot Pockets.

Recent advances in synthesis techniques yield InP-based QDs with optical properties comparable to those of benchmark Cd-based QDs, making InP-based QDs viable alternatives to toxic Cd-based QDs for applications such as quantum dot LEDs (QLEDs). However, QLEDs typically suffer from a loss of luminescence over time due to exposure of the QDs to ambient air. To avoid this, state-of-the-art hybrid barrier layers are explored consisting of alternating organic/inorganic layers. In this study, InP-based QD thin films and InP-based QDs embedded in Kraton polymers are encapsulated with a thin metal oxide barrier layer by atomic layer deposition (ALD). Specifically, Al2O3, TiO2, and ZnO thin films are deposited using trimethylaluminum (TMA), tetrakis(dimethylamino)titanium (TDMAT), and diethylzinc (DEZ), with H2O as the reactant. In situ photoluminescence (PL) is used to evaluate the optical response of the InP-based QDs during the ALD coating. The results show that ALD on pristine QD thin films causes degradation of luminescence, while this is not observed for polymer-embedded QDs. The long-term stability of the (ALD-coated) samples is investigated by accelerated degradation in a humidity chamber at a high temperature. Using a single Al2O3 ALD thin film as a capping layer for polymer-embedded QDs, greater stability of the QD-PL over a period of at least 300 h is found compared to pristine QD samples. A similar study is performed with InP-based QDs embedded in UV-patterned polymer (thiol-ene) structures, the so-called QD pockets, envisioned for use in on-chip quantum dot microLEDs. These QD pockets are purposefully designed for pick-and-place operations to reduce the complexity of the on-chip quantum dot microLED manufacturing process. The PL stability was significantly improved after incorporating Al2O3 ALD thin films, with these hybrid QD pockets showing no clear signs of degradation after 140 h. The combination of polymer embedding and ALD with the merits and scalability of the QD pocket structure is demonstrated to be an effective approach to improving the long-term QD stability and shows promise for the development of stable, InP-based on-chip quantum dot microLEDs.

Development of engineered Zn-MOF/g-C3N4 based photoelectrochemical system for real-time sensors and removal of naproxen in wastewater

Naproxen-contaminated water may lead to the accumulation of the drug in aquatic organisms and can pose high risks to an aquatic environment and human beings. Therefore, this work aimed to develop photoelectrochemical sensing and degradation of naproxen (NPX) using zinc-metal organic framework /graphitic carbon nitride thin film-based fluorine-doped tin oxide (Zn-MOF/g-C3N4/FTO) as anode material for the sensing and degradation of naproxen (NPX). The surface morphology, structure, surface property, surface area, optical property, photocurrent, and charge transfer kinetics abilities were studied using different techniques. The nanocomposites showed a superior photocurrent response (0.815 mA cm-2) compared to the original g-C3N4 (0.328 mA cm-2). The photo-anode made of Zn-MOF@g-C3N4/FTO displayed the highest photocurrent value, indicating that the alignment of the two semiconductor bands prevented the quick recombination of electron-hole pairs. Owing to these attractive features, the Zn-MOF/g-C3N4/FTO electrode was applied for photoelectrochemical detection of NPX using chronoamperometry. Interestingly, the nanocomposites-based FTO ascribed a lower detection limit (2.3 ng l-1) with a wide linear range concentration of NPX (0.5 to 200 µg l-1). Additionally, the analytical assessment of repeatability and reproducibility demonstrated robust performance, with commendable relative standard deviations (RSD%) of 2.54 % and 2.40 %, respectively. On the other hand, a remarkable degradation efficiency of 97.52 % was attained when employing a bias potential of 0.1 V during a 2 h photoelectrocatalytic oxidation of NPX. The degradation process was primarily driven by the active participation of holes and hydroxyl radicals in ring opening and subsequent cleavage of by-products. The notable effectiveness of this degradation can be attributed to the combined and synergistic effects of both electrochemical and photocatalytic degradation techniques. The current state demonstrates its effectiveness in the photoelectrochemical sensing and removal of NPX using MOF/g-C3N4 nanocomposites-based electrode materials in wastewater.

Characterization of thin oxide layers formed by Ti-Nb Alloy anodization

Ti-Nb alloys are gaining more prominence in the industrial and scientific environment due to their high biocompatibility, mechanical strength/weight ratio, and exceptional corrosion resistance compared to other metallic materials. Metals exhibiting this passivation characteristic are known as metal valves and may exhibit semiconductive or insulating oxides. Controlling the growth of distinct thickness layer films is possible through tunning anodization conditions. In this work, a Ti-Nb binary system is anodized, and the grown oxide layer is comprehensively characterized using ellipsometry based on its optical properties and thickness at different applied potentials. Confocal Microscopy assessed their surface roughness, and SEM/EDS probed the surface material's elemental composition. CF-LIBS successfully confirmed the 70/30 composition of the Ti-Nb alloy. Raman spectra have detected the presence of amorphous TiO2 and Nb2O5 at potentials higher than 80V, 100V, and 120V. Finally, a linear dependence of the oxide thickness with the applied potential was observed.

Design of an optically transparent ultrawideband absorber with high angular stability using ITO films.

In this paper, an optically transparency ultrawideband absorber with high angular stability is designed. The proposed absorber is composed of two different materials with indium thin oxide (ITO) conductive films and polydimethylsiloxane (PDMS) substrates. With the aid of a stacked structure design, the absorber has a 90% absorption band from 5 to 43.5 GHz and the fractional bandwidth reaches 158.7%. Also, for the TE mode, the absorption remains stable with the oblique incident angles reaching 50°. And similar angular stability can be observed for the TM mode from 0° to 70°. Besides, the thickness of the absorber is only 0.092 wavelength and transmittance within the visible band is 57.3%. For further verification, a prototype is fabricated and measured. Good agreements between the simulated and the measured results can be observed.

New insight on the formation of uneven oxide scales on AFA steel in supercritical CO2: Roles of recrystallization degree on the high temperature corrosion resistance

Uneven oxide scale is a common phenomenon in high-temperature corrosion, but the formation mechanism has not been fully uncovered. A new alumina-forming austenitic (AFA) stainless steel with superior corrosion resistance in 650°C/15 MPa SC-CO2, has been systematically investigated. It is demonstrated that the uneven oxide was formed by the significant impact of the recrystallization behavior of AFA steel on its microstructural evolution and subsequent corrosion behavior. Compared with the thin oxide scale, the thick oxide scale was caused by the relatively higher density of dislocations and grain boundaries of matrix resulting from delayed recrystallization, which facilitated the rapid outward diffusion of ions.

Photon echo on excitons for the development of nanoelectronic devices based on a quantum-size structures in a thin zinc oxide films

The relaxation decays of photon echo signals in thin zinc oxide films produced by magnetron sputtering have been studied. Echo signals are excited at a wavelength of 800 nm at transitions between quantum levels that arise when excitonic states are localized in quantum-sized structures in the two-photon absorption mode of laser pulses with a wavelength of 800 nm.

Giant Decrease in Interfacial Energy of Liquid Metals by Native Oxides.

Native oxides form on the surface of many metals. Here, using gallium-based liquid metal alloys, Johnson-Kendall-Roberts (JKR) measurements are employed to show that native oxide dramatically lower the tension of the metal interface from 724 to 10 mNm-1. Like conventional surfactants, the oxide has asymmetry between the composition of its internal and external interfaces. Yet, in comparison to conventional surfactants, oxides are an order of magnitude more effective at lowering tension and do not need to be added externally to the liquid (i.e., oxides form naturally on metals). This surfactant-like asymmetry explains the adhesion of oxide-coated metals to surfaces. The resulting low interfacial energy between the metal and the interior of the oxide helps stabilize non-spherical liquid metal structures. In addition, at small enough macroscopic contact angles, the finite tension of the liquid within the oxide can drive fluid instabilities that are useful for separating the oxide from the metal to form oxide-encased bubbles or deposit thin oxide films (1-5nm) on surfaces. Since oxides form on many metals, this work can have implications for a wide range of metals and metal oxides in addition to explaining the physical behavior of liquid metal.

Double-layer optical fiber interferometer with bio-layer-modified reflector for label-free biosensing of inflammatory proteins

This work discusses label-free biosensing application of a double-layer optical fiber interferometer where the second layer tailors the reflection conditions at the external plain and supports changes in reflected optical spectrum when a bio-layer binds to it. The double-layer nanostructure consists of precisely tailored thin films, i.e., titanium (TiO2) and hafnium oxides (HfO2) deposited on single-mode fiber end-face by magnetron sputtering. It has been shown numerically and experimentally that the approach besides well spectrally defined interference pattern distinguishes refractive index (RI) changes taking place in a volume and on the sensor surface. These are of interest when label-free biosensing applications are considered. The case of myeloperoxidase (MPO) detection—a protein, which concentration rises during inflammation—is reported as an example of application. The response of the sensor to MPO in a concentration range of 1 × 10−11–5 × 10−6 g/mL was tested. An increase in the MPO concentration was followed by a redshift of the interference pattern and a decrease in reflected power. The negative control performed using ferritin proved specificity of the sensor. The results reported in this work indicate capability of the approach for diagnostic label-free biosensing, possibly also at in vivo conditions.

Oxidation of a zirconium nitride multilayer-covered knee implant after two years in clinical use

The surface composition and microstructure of an up to 5 µm thick multilayer on a knee implant were investigated. When the implant was explanted after approximately two years of clinical use due to failure from aseptic loosening, the topmost ZrN layer was found to be oxidized. Interestingly, only the non-articulating area was visibly oxidized (color change).Up until then, the formation and characteristics of the oxide and its influence on the tribological performance remained uncertain. The oxide was thoroughly analyzed using transmission electron microscopy (TEM) and atom probe tomography (APT). The articulating and non-articulating areas were compared with an as-fabricated implant, which served as a reference. The results show that a thin oxide was also present on the articulating surface. All measured oxides were thicker than expected from native oxidation. The oxygen content of the majority of the oxide, measured with energy dispersive X-ray spectroscopy (EDS) and APT, was lower than required for the stable ZrO2 form. Underneath the oxide, the ZrN layer remained unaffected, demonstrating the oxide's effective passivating behavior against further oxidation. No cobalt from the substrate was detected within the ZrN layer, proving the multilayer's excellent barrier function against ion release from the base metal. Statement of significanceIn our aging society, the use of artificial knee implants is widespread. Implant failure is not only costly, but often connected with pain for the patient and inevitably involves the implantation of a new joint. Hence, understanding the origin of joint failure is of high importance to extend the lifetime of the implant. In this research, we investigate the influence of a surface oxide, formed on an explant which failed after ∼ 2 years, on the multilayer stability. As a novelty, we focus not on the wear of the polyethylene gliding surface but on the formed oxide. The use of high-resolution analysis techniques allowed us to get a glimpse on the ongoing mechanisms at the explants surface.

Structural and morphological properties of CeO2 films deposited by radio frequency magnetron sputtering for back-end-of-line integration

Cerium oxides have potential applications ranging from low-temperature gas sensing to photodetection. A back-end-of-line integration of the material into complementary metal-oxide-semiconductor device fabrication processes has many advantages but places limits on material deposition, most notably the thermal budget for deposition and annealing. Here, we investigate thin cerium oxide films deposited by radio frequency (RF) magnetron sputtering at substrate temperatures of 300 °C and RF magnetron powers between 30 W and 70 W without any post-deposition annealing steps. Our investigation of the structural and morphological properties reveals a columnar texture of the thin films, and we find that the material is composed predominantly of CeO2 (111), with a large degree of crystallinity. We discuss implications for resistive gas sensing applications.

Fabrication of Self-Assembled Graphene Oxide Film and Its Application in Aqueous Zinc Metal Batteries.

Fabrication of well-dispersed thin graphene oxide (GO) films (GOFs) has always been a challenge. Herein, a quick preparation method for GOFs was developed using our homemade GO with a large lateral size. The film can be prepared in less than 2 h via a metal framework-induced self-assembly process. The thickness of the films can be as thin as ∼15.5 μm, which will be thinner with compression. When it is used as a flexible modification layer on the Zn metal for aqueous Zn-ion batteries, Zn can grow along the [010] direction in plane and stack orderly along the [002] direction even on the Cu substrate with GOF through epitaxial plating owing to negligible lattice mismatch between the (002) plane of Zn and the hexagonal ring [also (002) plane for graphite] of GO. Meanwhile, the rich O groups on the GO film can provide abundant zincophilic points and promote uniform distribution of Zn2+ around the anode. Finally, dendrite-free and dense Zn stripping/plating can be achieved and well remained. The GOF@Zn symmetric cell reveals long cyclic stability of 1300 h at 1 mA cm-2 and 1 mA h cm-2. It still can remain at 350 h even at a very high current density of 10 mA cm-2 accompanied by a high areal capacity of 10 mA h cm-2. With the same plating amount of 5 mA h cm-2, the thickness of the plated Zn is only ∼10 μm with GOF modification, very close to the theoretical value of 8.54 μm, much thinner than that without GOF (∼18 μm), indicating very dense deposition. Full cells assembled with the GOF@Zn anode and the MnO2 cathode exhibit a capacity retention rate of 71% over 1000 cycles at 0.7 A g-1, showing much better cycling performance than that using bare Zn.

Surface decoration of Nb2O5 hollow fibers by graphene oxide for enhanced photocatalytic degradation of methylene blue

AbstractThis paper describes the fabrication of ceramic Nb2O5 hollow fibers covered by a thin graphene oxide (GO) layer using the vacuum‐assisted dip‐coating process for the efficient photocatalysis degradation of methylene blue (MB) under UVC light irradiation. Pristine and GO‐coated Nb2O5 hollow fibers were evaluated for photocatalytic degradation at different initial dye concentrations and pH values. A photodegradation of 66.4% of the dye molecules was achieved using the pristine Nb2O5 hollow fibers at 57.4 ± 0.1 mg mL1, initial MB concentration of 10 mg L−1, and pH of 11. Under the same experimental conditions, the GO‐coated Nb2O5 hollow fibers degraded 100% of the MB molecules. Additionally, the GO‐coated Nb2O5 hollow fibers were successfully reused for four reaction cycles and exhibited suitable long‐term stability. Thus, the proposed ceramic Nb2O5 hollow fibers with a surface decorated by a GO layer presented suitable characteristics for use as a photocatalyst in MB degradation.

Dewetting-driven printing of thin metal oxide films

Dewetting-driven printing of thin metal oxide films

The influence of pH electrolyte on the electrochemical deposition and properties of cerium oxide thin films

Thin cerium oxide layers cathodically deposited on zinc were studied. These electrochemically deposited coatings provide effective corrosion protection and require less deposition time compared to chemical conversion coatings. The kinetics of their formation depend on various factors, such as temperature, applied current density, electrolyte composition, pH, and agitation. In this study, the effect of bath solution pH was investigated, with coatings produced at room temperature from aqueous cerium nitrate solutions. Chronopotentiometry, linear sweep voltammetry, and electrochemical impedance spectroscopy (EIS) were used to monitor the deposition process, while scanning electron microscopy and energy-dispersive spectroscopy were performed to characterize the deposits. Corrosion resistance was evaluated through potentiodynamic tests in a 3.5% NaCl solution. The results indicate that the electrolyte pH significantly influences the cerium electrodeposition process. Based on the findings, the cerium oxide coating obtained from a pH 4 solution exhibited lower corrosion current density, higher polarization resistance, and superior anti-corrosion performance.

Corrosion of stainless steel and molybdenum used as PCC in Na//Sb-Bi liquid metal batteries under cycling conditions

Material compatibility is a major challenge in the development of liquid metal batteries. In this study, the corrosion behavior of two candidate positive current collector materials, austenitic stainless steel and molybdenum, in Na//SbBi9 liquid metal batteries is investigated. In-situ corrosion in operating cells is compared with static corrosion in SbBi9 (corresponding to the fully charged state) and Na0.30Sb0.07Bi0.63 (representing the fully discharged state) at 450 °C. Stainless steel shows a much better corrosion resistance in Na-Sb-Bi alloy (corrosion depth below 1 μm after 750 h static exposure) than in SbBi9 (7–9 μm corrosion layer) thanks to the formation of a thin oxide layer. The corrosion under cycling conditions shows similar characteristics (formation of solid Fe-Cr-Ni-Sb compounds), though accelerated, as static exposure to SbBi9. Molybdenum exhibits a very good corrosion resistance both in static and in cycling conditions, showing merely a minor dissolution into the adjacent alloy.