Vacuum Annealing Research Articles

Chromium–Aluminum Coatings for Oxidation Protection of Titanium–Aluminum Intermetallic Alloys

This article explores the utilization of cathodic-arc deposition Cr-Al overlay coatings as oxidation protection for Ti-Al-Nb intermetallic alloys. The primary objective is to investigate PVD Al-Cr coatings deposited via cathodic-arc deposition without subsequent vacuum annealing. The microstructure, phase, and chemical composition of the coatings were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction analysis. Isothermal exposure of samples in a laboratory air furnace was conducted, revealing the efficacy of Cr-Al coatings in protecting the Ti49-11Al-40Nb-1.5Zr-0.75V-0.75Mo-0.2Si (mass%) intermetallic alloy VTI-4 against oxidation. The findings highlight that the as-deposited coatings possess a layered structure and contain Al-Cr intermetallics. Post-exposure to the furnace without prior vacuum annealing results in coatings exhibiting a porous microstructure, raising concerns regarding oxidation protection. This investigation of Cr-Al coatings on a VTI-4 alloy substrate yields valuable insights into their nanolaminate structure and challenges associated with aluminum droplet fractions. The proposed additional vacuum heat treatment at 650 °C for 500 h effectively homogenizes the coating, leading to predominant Cr2Al and Ti-Al phases. Additionally, the formation of diffusion layers at the “coating–substrate” interface and the presence of oxide barriers contribute to the coatings’ heat resistance. Our research introduces possibilities for tailoring coating properties for specific high-temperature applications in aerospace, energy, or industrial contexts. Further refinement of the heat treatment process offers the potential for developing advanced coatings with enhanced performance characteristics.

Influence of heat treatment on the structure and mechanical properties of zirconium dioxide crystals partially stabilized by samarium oxide

The effect of high-temperature treatment in different media on the phase composition, microhardness and fracture toughness of (ZrO2)1-х(Sm2O3)х crystals with x = 0.02÷0.06 has been studied. The crystals have been grown using direction melt crystallization in a cold skull. The crystals have been heat treated at 1600 °C for 2 h in air and in vacuum. The phase composition of the crystals has been studied using X-ray diffraction and Raman scattering. We show that samarium cations enter the ZrO2 lattice mainly in a trivalent charge state and do not change their charge after air or vacuum annealing. The as-annealed phase composition has changed in all the test crystals except for the (ZrO2)0.94(Sm2O3)0.06 composition. After air or vacuum annealing the (ZrO2)1-x(Sm2O3)x crystals with 0.002 ≤ x ≤ 0.05 contain a monoclinic phase. The (ZrO2)0.94(Sm2O3)0.06 crystals contain two tetragonal phases (t and t´) with different tetragonality degrees. After air or vacuum annealing of the (ZrO2)0.94(Sm2O3)0.06 crystals the lattice parameters of the t and t´ phases change in opposite manners, suggesting that the tetragonality degree of the t phase increases whereas the tetragonality degree of the t´ phase decreases. The microhardness and fracture toughness of the as-annealed crystals depend on the Sm2O3 concentration in the solid solutions. The formation of the monoclinic phase in the (ZrO2)1-х(Sm2O3)х crystals with 0.037 ≤ x ≤ 0.05 significantly reduces the microhardness and fracture toughness of the crystals. Annealing of the (ZrO2)0.94(Sm2O3)0.06 crystals triggers more efficient hardening mechanisms and thus increases the fracture toughness of the crystals. We show that air or vacuum annealing of the (ZrO2)0.94(Sm2O3)0.06 crystals increases the fracture toughness of the crystals by 1.5 times as compared with that of the as-grown crystals.

Influence of vacuum annealing on mechanical characteristics of focused ion beam fabricated silicon nanowires

This paper describes the influence of vacuum annealing on the mechanical characteristics of silicon (Si) nanowires (NWs) fabricated using focused ion beam (FIB) technologies. Two types of Si NWs having a cross-sectional one-side length or diameter ranging from 19 to 447 nm are prepared using the direct milling and Ga ion doping functions of FIB. The Si NWs prepared are annealed at 400–700 °C in high vacuum for 10 min, followed by quasi-static uniaxial tensile testing using a microelectromechanical system based tensile test system in a scanning electron microscope. All the Si NWs fracture in a brittle manner. Young's modulus of submicrometer-sized Si NWs shows both annealing and specimen size influences in the range from 120 to 170 GPa, whereas that of nano-sized Si NWs shows only annealing influence in the range from 60 to 110 GPa. Tensile strength scatters greatly, ranging from 1.0 to 7.2 GPa, which increases with increasing the NW size. A transmission electron microscope and an atomic force microscope suggest that, by annealing, recrystallization happens in the damaged layer introduced by FIB milling and the NW surface morphology changes due to its recrystallization and gallium (Ga) ion evaporation. Fracture origin is discussed through the comparison between surface roughness and crack length estimated by the Griffith theory of brittle fracture.

Marigold flower like Co3O4 nanoparticles as high performance electrodes for supercapacitors

Transition metal oxides promised as electrode materials for supercapacitors have received much interest, especially cobalt oxide (Co3O4) nanoparticles. However, the low intrinsic electrical conductivity and aggregation of Co3O4 nanoparticles limit their electrochemical performance and impede the commercialization of these electrode materials. The present study describes a simple, and cost-effective solution combustion approach for producing marigold Co3O4 at 300 °C. Further, the effect of vacuum annealing on the microstructural and electrochemical properties is studied to explore the nanostructured samples of Co3O4 as potential electrode material. The electrochemical nature of prepared marigold Co3O4 nanoparticles in 3 M KOH aqueous electrolyte has the highest specific capacitance of 603 Fg−1 at a scan rate of 1 mVs−1 with greater electrochemical stability even after 5000 cycles. The possible reasons for a decrease in specific capacitance on annealing of as prepared Co3O4 at 300 °C are explored in this paper and some significant reasons are highlighted.

Modulations for Quantum Electronic Material Transports by Vacuum Annealing Methods

Gapless linear band structure quantum electronic materials play important roles in quantum computing developments due to their novel superb electronic transport properties and two-dimensional (2D) gateable device possibility. However, the sensitive surface of quantum electronic materials easily reacted with ambient air molecules so as to change their intrinsic transport properties. We review a series of our works to show the importance of surface reactions in quantum electronic materials, such as graphene. By using different electronic transport facilities and in situ vacuum annealing methods, we are able to gently clean the absorbed air molecules on graphene so as to change the carrier densities and the electronic transport properties, which is a great improvement for 2D-quantum material-based quantum chips and computing devices.

Electrical resistivity of coatings of quasicrystalline and crystalline phases of the Ti—Zr—Ni system in the temperature range 4–300 K

The temperature dependence of the electrical resistivity in the temperature range from 4.4 to 300 K for Ti41Zr41Ni18 (at. %) thin coatings of different crystal perfection and phase composition was studied. The coatings were deposited by magnetron sputtering with subsequent vacuum annealing in various modes ensuring the formation of several heterophase combinations, which included 1/1 and 2/1 approximation phases, a quasicrystalline icosahedral phase, a Laves phase (Ti, Zr)2Ni, and an α-Ti (Zr) solid solution. The structure before and after annealing was studied by X-ray diffractometry. It was established that coatings with a predominant content of amorphous, quasicrystalline, or approximant 2/1 phases have a temperature coefficient of resistance less than zero, while samples with a predominance of crystalline phases demonstrate characteristic metallic conductivity. The temperature dependence of the electrical resistivity of the Ti41Zr41Ni18 quasicrystalline coating turned out to be similar to the dependence in bulk samples of the Ti40Zr40Ni20 composition. The electrical resistivity of the approximant 2/1 phase with a low content of the additional Laves phase in the film has an almost constant value in the entire investigated temperature range.

Structure of monolayer iron nitride islands on Cu(001) revisited

We revisited the structure of monolayer iron nitride islands grown on Cu(001) using the well-established procedure, i.e. by bombarding the substrate with low-energy N+ ions, depositing Fe at room temperature and annealing in ultra-high vacuum (UHV). The geometric parameters of the obtained iron nitride were matching those of the “Fe2N” phase described in the literature and constituting the middle-plane-cut of the γ′-Fe4N unit cell. However, the atomic structure was found to exhibit an out-of-plane corrugation not reported by other authors so far. Moreover, the islands had an Fe1.3N stoichiometry and were characterized by a much higher work function value than the one predicted theoretically for the Fe2N phase. Based on these findings, we propose a new structural model for monolayer iron nitride on Cu(001), in which an additional N atom resides on top of every second Fe atom in each atomic row of the Fe2N. We also show that the Fe1.33N islands may be reduced to species with Fe2N stoichiometry through the exposure to O2 at room temperature and subsequent annealing in UHV. Thus, direct formation of the Fe2N phase under specific experimental conditions, as indicated by other authors, may be also possible.

Phase decomposition of AlCrFeCoNiCu0.5 HEA thin films by vacuum annealing

The most attractive advantages of high entropy alloy (HEA) thin films are their excellent properties, such as high strength and high corrosion and oxidation resistance, with a lower material cost. However, the thermal stability of the HEA thin films is always controversial. This is critical since the thermal stability of metals and alloys is closely related to the material's performance at high temperatures and also determines the application field of the material. The question of how will the nanocrystalline high entropy alloy thin film perform in terms of thermal stability needs to be clarified urgently. In this research, the thermal stability of AlCrFeCoNiCu0.5 HEA thin film fabricated by cathodic arc deposition was investigated at 500 °C as a function of time during vacuum annealing. X-Ray Diffraction (XRD), High-Resolution Transmission Electron Microscopy (HRTEM) and Transmission Kikuchi Diffraction (TKD) were applied to analyze the chemistry and microstructure of HEA thin films in detail. The results showed that there was no obvious change in the elemental compositions of the films after annealing, but the elemental distribution of the annealed films was different from the as-deposited film, especially at the film surface and film-substrate interface for the 24 h-annealed sample. The existence of the FeCo phase with B2 structure was a significant sign to demonstrate that the spinodal decomposition occurred in the single face-centered-cubic (FCC) phase matrix of the film during annealing. Simultaneously, the segregation of Cu and Cr near the film-substrate interface and the penetration of Ni and Cu towards the Si substrate were clearly observed. These unusual phenomena indicated that the thermal stability of HEA was not always excellent. Also, it was noticed that a few Kirkendall voids forming at the film-substrate interface after 24 h of annealing would affect the adhesion of the film. Additionally, heat recovery and recrystallization were achieved by 500 °C annealing, which were confirmed by the decrease of lattice parameter and the increase of grain size in the 24 h-annealed thin film. Furthermore, the hardness and elastic modulus of the thin films before and after annealing were measured by nanoindentation. The results showed all the thin films exhibited excellent mechanical properties, and the optimal hardness and elastic modulus of 7.7 ± 0.3 GPa and 183.9 ± 4.4 GPa were obtained after 3 h-annealing.

“Anomalous” diffusion in multi-layer silicide systems

The transition metal silicide coatings have excellent oxidation resistance. In the high-temperature oxidization environment, the “anomalous” diffusion phenomenon of the reverse concentration gradient occurs in the multilayer silicide coating structure, which has a significant impact on the coating degradation. This study is to explore the physical mechanism of “anomalous” diffusion phase transformation in the MoSi2–NbSi2 bilayer silicide coating on the Nb alloy substrate. Through vacuum annealing experiments, combined with micro-Raman spectroscopy and electron probe microanalysis measurements, the diffuisonal phase transformation of multilayer silicide coating in the oxygen-free environment at high temperatures was studied. By decoupling the oxidation and diffusion, the experiments indicate that high-temperature oxidation is not the dominant driving factor for the “anomalous” diffusion of atoms. The thermodynamic analysis reveals that the reduction in the nucleation barrier of the silicide-poor layer due to multicomponent solid solution and the non-uniform distribution of component chemical potential provide the driving force for the “anomalous” diffusion growth. Based on the diffusion kinetic modeling, the simulation of diffusion-controlled phase transformation in multilayer silicide coating was carried out, and the effect of tracer diffusion coefficients on the growth of the silicide-poor phase was analyzed. The research will have guiding significance for the recognition of failure mechanisms of silicide coating systems and performance improvement.

Preparation of pure hydrogenated amorphous silicon film via PECVD method as anode materials for high-performance lithium-ion batteries

In this paper, plasma-enhanced chemical vapor deposition (PECVD) is used to prepare a nano-scale pure hydrogenated amorphous silicon thin film anode, which improves the problem of large volume effect of traditional silicon-based anode materials during the charge and discharge process of lithium-ion batteries. Among them, the thinnest 120 nm pure silicon film still has a high specific capacity of 1254.6 mAh g−1 after 200 cycles at 0.5C (1C = 4.2 A g−1), and also has an excellent performance of 848.2 mAh g−1 after a large rate of charge and discharge of 5C. To give consideration to the performance and obtain a certain mass load at the same time, 170 nm pure silicon film was selected for vacuum annealing treatment at different temperatures to release the non-uniform compression stress during the deposition of hydrogenated amorphous silicon, and a more stable film structure was constructed, which further improved the performance of silicon film. Among them, the best performance is held at 100 °C for 5 h, and the reversible specific capacity of 1172.7 mAh g−1 is still maintained at 200 cycles at 0.5C, and the reversible specific capacity of 1131.6 mAh g−1 is also available at a super high rate of 10C.

On the determination of the thermal shock parameter of MAX phases: A combined experimental-computational study

Thermal shock resistance is one of the performance-defining properties for applications where extreme temperature gradients are required. The thermal shock resistance of a material can be described by means of the thermal shock parameter RT. Here, the thermo-mechanical properties required for the calculation of RT are quantum-mechanically predicted, experimentally determined, and compared for Ti3AlC2 and Cr2AlC MAX phases. The coatings are synthesized utilizing direct current magnetron sputtering without additional heating, followed by vacuum annealing. It is shown that the RT of both Ti3AlC2 and Cr2AlC obtained via simulations are in good agreement with the experimentally obtained ones. Comparing the MAX phase coatings, both experiments and simulations indicate superior thermal shock behavior of Ti3AlC2 compared to Cr2AlC, attributed primarily to the larger linear coefficient of thermal expansion of Cr2AlC. The results presented herein underline the potential of ab initio calculations for predicting the thermal shock behavior of ionically-covalently bonded materials.

Thermal Stability of Oxidation-Resistant Ta-Zr-Si-B-N and Ta-Zr-Si-B-C Coatings under In Situ TEM Heating and Vacuum Annealing

Amorphous Ta-Zr-Si-B-C and Ta-Zr-Si-B-N coatings were deposited by magnetron sputtering using a ceramic target in Ar + C2H4 and Ar + N2 reaction media. Thermal stability under in situ TEM heating, vacuum annealing and nanoindentation, as well as the effect of heating on structural-phase transformations in coatings and their mechanical characteristics, have been studied. The results showed that the heating of amorphous Ta-Zr-Si-B-C and Ta-Zr-Si-B-N coatings in a TEM column leads to precipitation h-TaSi2 and c-TaC crystalline phases at a temperature of 600 °C and h-Ta5Si3 and c-TaN at a temperature of 1000 °C, respectively. Similar structural-phase transformations were revealed as a result of vacuum annealing. An increase in temperature from 20 to 1000 °C led to a decrease in the hardness of the carbon-containing coating from 21 to 16 GPa as a result of stress relaxation. For the Ta-Zr-Si-B-N coating at a temperature of 1000 °C, an increase in hardness was observed from 18 to 27 GPa, which is associated with the crystallization of the coating, with the formation of a nanocomposite structure with h-Ta5Si3 and c-TaN crystallites of 6–10 nm in size and an a-Si(Zr,B)N amorphous region.

Quasi-In Situ XPS Insights into the Surface Chemistry of Garnet-Type Li6.4La3Zr1.4Ta0.6O12 Solid-State Electrolytes: The Overlooked Impact of Pretreatments and a Direct Observation of the Formation of LiOH.

Garnet-type Li6.4La3Zr1.4Ta0.6O12 (LLZTO) is a highly promising solid-state lithium metal battery electrolyte due to its exceptional ionic conductivity and electrochemical stability. However, when exposed to air, a passivation layer can be spontaneously formed on the garnet-type electrolyte, deteriorating its wettability with metallic lithium (Li) and impeding the lithium ion transfer at the Li-garnet electrolyte interface. The passivation layer is considered a critical issue for garnet-type solid electrolytes. Despite intensive research, the formation mechanism of the passivation film remains poorly understood. The key to elucidating the formation mechanism is to obtain a pristine garnet electrolyte surface and study how the pristine garnet electrolyte interacts with air. In this study, different passivation layer removal pretreatments were performed to expose pristine garnet electrolytes, and their impacts on the samples were systematically studied. The results reveal the overlooked negative impacts of vacuum annealing and acid treatment on LLZTO, which are indicated by the severe loss of Li and O and the formation of additional Li-depleted metal oxides. It was confirmed that argon annealing is the only viable approach to remove the passivation layer without introducing concomitant contaminations to LLZTO. Based on this method, we directly evidenced the formation of LiOH on LLZTO under rarefied air using quasi-in situ X-ray photoelectron spectroscopy. It was confirmed that the loss of Li and O ions, rather than Li+/H+ exchange, drives the formation of LiOH in the passivation layer. These results not only provide a better understanding of the surface and interface chemistry of LLZTO but also reveal a reliable surface treatment for the LLZTO sample.

Unraveling the role of nanocrystalline in amorphous nanoporous FeCoB catalysts for turning oxygen evolution activity and stability

The sluggish kinetics and high-power consumption of the oxygen evolution reaction (OER) are recognized as major barriers in electrocatalysis. Therefore, exploring cheap and highly-efficient OER electrocatalysts is highly desired for improving energy storage and conversion. Related Fe-based materials have been widely applied in OER electrocatalyst field due to their excellent OER activity. Herein, we adopt the vacuum annealing and electrochemical dealloying methods to produce a self-supporting np-Fe40Co40B20-800-5min catalyst enriched with nanocrystalline. The self-supporting np-Fe40Co40B20-800-5min catalyst exhibits superior OER performance with an overpotential of 315 mV at a current density of 10 mA cm−2 and a small Tafel slope of 26 mV dec−1. The overpotential of the np-Fe40Co40B20-800-5min catalyst is boosted by more than 20 percent over that obtained np-Fe40Co40B20 catalyst. The active intermediates were explored by in situ Raman under catalytic conditions. The in-depth mechanism research suggests that the nanocrystalline may serve as an advantageous electrocatalytic species in amorphous np-Fe40Co40B20-x-ymin catalyst. This study offers a novel approach to promoting catalytic properties in an amorphous np-Fe40Co40B20-800-5min catalyst based on enriched nanocrystalline.

Investigation of the Effect of Vacuum and Air Annealing on the Structural, Optical and Electrical Properties of Radio Frequency Sputtered WO<sub>3</sub> Thin Films

Thin films of tungsten oxide were deposited on glass substrates by the radio frequency (RF) reactive sputtering from a high purity tungsten metal target (99.9%) with a diameter of 10 cm. The reactive sputtering was carried out in an argon-oxygen gas mixture containing 20% of O2 and 80% of Ar. The used RF power is 200 W while fixing the deposition time at 120 min. Finally, the prepared films were annealed at different temperatures (350 °C, 400 °C, 450 °C, 500°C and 550 °C) for 1 hour under air and under vacuum. X-ray diffractograms showed that the deposited thin films crystallized in Hexagonal/Monoclinic WO3 phase. It was found that the crystallite size varies with the annealing temperature and the lattice parameters is a= 7.3064Å, b = 7.5292Å, c = 7.6875Å and a=b= 7.3242Å, c= 7.6624 Å, for h-WO3 and m-WO3 structures, respectively. Scanning Electron Microscopy (SEM), Raman spectra confirmed the formation of WO3 thin films. In addition, optical transmittance data revealed that the optical bandgap of the films decreases with increasing the annealing temperature. Electrical measurements revealed that annealing in air results in more resistive samples, which should be taken into account in future investigations, especially as buffer layers for efficient photovoltaic solar cells. Keywords: Vacuum, Tungsten oxide, Raman spectroscopy, RF Sputtering method, RF Power, Annealing temperature.

Influence of vacuum annealing on the structure and phase composition of rapidly solidified hydrogenated orthorhombic titanium alloy

Rapidly solidified alloy based on the orthorhombic Ti2AlNb intermetallic compound is studied in this work as an excellent material for hydrogen absorption and synthesis of powder by hydrogenation-dehydrogenation method. Vacuum annealing and dehydrogenation are indispensable for the formation of the final microstructure and phase composition of the powder. We investigated the influence of vacuum annealing on the structure and phase composition of an alloy based on the Ti2AlNb phase which was obtained by rapid solidification of the melt and then hydrogenated up to 0.2 and 0.65 wt% of hydrogen. The hydrogenated alloy was compared to the non-hydrogenated one subjected to the same vacuum treatment. Vacuum dehydrogenation allows retaining the initial fine-grained structure of the alloy with the β-grain size of less than 25 μm. Also, it leads to a partial decomposition of the metastable β-phase and precipitation of acicular particles of the orthorhombic phase inside the grains and equiaxed particles along the grain boundaries. The morphology of the orthorhombic phase particles changes insignificantly with an increase in the vacuum annealing temperature, while the concentration of the introduced hydrogen and the dehydrogenation temperature have a great influence on their volume fraction.

Dielectric and room temperature ferromagnetism in vacuum annealed Bi(Zn0.5Zr0.5)O3 modified PbTiO3 ceramics

Polycrystalline solid solutions of (1-x)PbTiO3-(x)Bi(Zn0.5Zr0.5)O3[x = 0.10, 0.20, 0.30] have been synthesized by using solid state reaction method and followed by air annealing (AA)/ vacuum annealing (VA). All the samples show single phase perovskite structure with tetragonal symmetry (P4mm). Structural parameters are calculated using the Rietveld refinement technique. With the help of Scanning Electron Microscope (SEM), the surface morphology of all the samples is recorded at room temperature. The influence of VA on dielectric parameters such as dielectric constant and tangent loss of the synthesized samples are studied and compared with that of AA samples. These results unfold superior dielectric properties of VA samples as compared to AA samples. Intriguingly, the VA samples exhibit exotic ferromagnetism in non-magnetic PbTiO3–Bi(Zn0.5Zr0.5)O3 samples, transforming these into room temperature magneto-electric multiferroics. Besides, both the ferroelectric and ferromagnetic order parameters were found to increase with the increase in Bi(Zn0.5Zr0.5)O3 doping in PbTiO3. The enhanced physical properties witnessed in VA PbTiO3–Bi(Zn0.5Zr0.5)O3 samples localized hopping of charge carriers confined to the grain.

Effect of annealing on focused ion beam induced surface damages in silicon analyzed by micro-Raman spectroscopy

In this paper, we describe Raman spectroscopic study for evaluating the influence of vacuum annealing on the surface modification of the focused ion beam (FIB) induced damaged layer on a single crystalline Si (c-Si) substrate. The damaged layer consisting of amorphous silicon (a-Si) with implanted Ga ions is formed after irradiating FIB onto the c-Si surface. After vacuum annealing at 700 °C for 10 s, the Raman spectrum peak of poly crystalline Si (p-Si) appears. With increasing annealing time, the spectral parameters, peak shift, peak intensity, and full width at half maximum (FWHM), for p-Si and c-Si change. Through the comparison between the phase fraction of a-Si, p-Si, and c-Si in the FIB damaged layer and the mechanical properties of the FIB-processed Si nanowires obtained in the quasistatic tensile testing, a recovery of the damaged layer by annealing is discussed.

Effect of CrMoN addition on the thermal stability and cyclic impact resistance of TiVN coatings

By adding V atoms to TiN, the tribological and mechanical properties of TiVN coatings are improved. Multilayered coatings, rather than monolayered ones, may further enhance the mechanical properties and thermal stabilities of TiVN. Therefore, an approach was employed in this study to synthesize gradient-and-multilayered CrMoN/TiVN coatings through vacuum arc ion plating. During the impact fatigue test that utilized a cyclic loading device, the correlation between cyclic impact resistance and coating structures of the deposited coatings were evaluated. Vacuum annealing and high temperature oxidation at temperatures exceeding 600 °C were used to assess the thermal stability of the coatings. Although the as-deposited TiVN coating achieved the highest hardness of 30.2 ± 2.5 GPa, the CrMoN/TiVN multilayer coating only experienced a slight decrease to 29.1 ± 2.2 GPa, which exceeded the solid solution quaternary CrMoTiVN mixture rule prediction. When compared to the high-hardness monolayered TiVN and the low-hardness CrMoN, the CrMoN/TiVN multilayer coatings demonstrated the best resistance to cyclic impact. The TiVN coating displayed the worst oxidation resistance, as shown by the emergence of elongated vanadium-rich Ti-V oxide slats on the surface after oxidation. The CrMoN coating exhibited higher oxidation resistance than TiVN, and small granular chromium oxides formed on the surface beyond 700 °C. The addition of CrMoN to TiVN to form CrMoN/TiVN resulted in improved oxidation resistance by inhibiting the oxidation of TiVN. A different oxidation behavior was found for the CrMoN/TiVN coatings. The design of gradient-and-multilayered CrMoN/TiVN coatings is proven to be advantageous for applications that aim to enhance the thermal stability and cyclic impact resistance of mechanical tools.

Modulation of GaAs nanowire growth by pre-treatment of Si substrate using a Ga focused ion beam

We reveal a novel phenomenon observed after self-catalytic growth of GaAs nanowires (NWs) on Si(111) substrates treated with a Ga focused ion beam (FIB). Depending on the ion dose, NW arrays with various geometrical parameters can be obtained. A minor treatment of the substrate enables a slight increase in the surface density of NWs relative to an unmodified substrate area. As the ion dose is increased up to ∼0.1 pC μm−2, the growth of GaAs NWs and nanocrystals is suppressed. However, a further increase in the ion dose stimulates the crystal growth leading to the formation of extremely thin NWs (39 ± 5 nm) with a remarkably high surface density of up to 15 μm−2. Resting upon an analysis of the surface structure before and after stages of ion-beam treatment, ultra-high vacuum annealing and NW growth, we propose a mechanism underlying the phenomenon observed. We assume that the chemical interaction between embedded Ga ions and a native Si oxide layer leads either to the enhancement of the passivation properties of the oxide layer within FIB-modified areas (at low and middle ion doses), or to the etching of the passivating oxide layer by excess Ga atoms, resulting in the formation of pores (at high ion doses). Due to this behavior, local fabrication of GaAs NW arrays with a diverse range of characteristics can be implemented on the same substrate. This approach opens a new way for self-catalytic growth of GaAs NWs.