Tailoring Mechanical and Optical Properties of Sputtered SiNx/BN Coatings.

The swift evolution of contemporary electronics products, such as flexible screens and wearable electronic devices, highlights the significance of flexible protective coatings, which combine superior mechanical and optical properties. Even though the recently developed polymer protective coatings can satisfy requirements for flexibility and transparency, their intrinsic nature often results in a hardness below 1 GPa, rendering them susceptible to scratches. On the other hand, traditional inorganic coatings, known for their high hardness and transparency, fall short of meeting flexibility requirements. In the present study, a SiNx/BN periodical nanolayered coatings (PNCs) structure has been tailored to achieve high mechanical durability, transparency, and flexibility. In SiNx/BN PNCs, the optical and mechanical properties of the single-layer SiNx film are crucial to the overall performance of the PNCs. Therefore, pulse direct current (DC) magnetron sputtering was optimized first to enhance the ionization efficiency of Si and N, thereby promoting their reaction and diminishing the presence of elemental silicon in SiNx. The effects of the pulse frequency and duty cycle on SiNx were evaluated. Additionally, the influence of the thickness ratio and modulation periods on the overall performance of the SiNx/BN PNCs was investigated. As a result, a SiNx/BN coating with sapphire-grade hardness, almost no optical absorption in the visible-near-infrared (vis-NIR) range, high wear resistance, and exceptional flexibility was demonstrated.

X-Ray Calc 3: improved software for simulation and inverse problem solving for X-ray reflectivity.

This work introduces X-Ray Calc (XRC), an open-source software package designed to simulate X-ray reflectivity (XRR) and address the inverse problem of reconstructing film structures on the basis of measured XRR curves. XRC features a user-friendly graphical interface that facilitates interactive simulation and reconstruction. The software employs a recursive approach based on the Fresnel equations to calculate XRR and incorporates specialized tools for modeling periodic multilayer structures. This article presents the latest version of the X-Ray Calc software (XRC3), with notable improvements. These enhancements encompass an automatic fitting capability for XRR curves utilizing a modified flight particle swarm optimization algorithm. A novel cost function was also developed specifically for fitting XRR curves of periodic structures. Furthermore, the overall user experience has been enhanced by developing a new single-window interface.

Tunable Molecular Sieving by Hierarchically Assembled Porous Organic Cage Membranes with Solvent-Responsive Switchable Pores.

Molecular separations involving solvents and organic impurities represent great challenges for environmental and water-intensive industries. Novel materials with intrinsic nanoscale pores offer a great choice for improvement in terms of energy efficiency and capital costs. Particularly, in applications where gradient and ordered separation of organic contaminants remain elusive, smart materials with switchable pores can offer efficient solutions. Here, we report a hierarchically networked porous organic cage membrane with dynamic control over pores, elucidating stable solvent permeance and tunable dye rejection over different molecular weights. The engineered cage membrane can spontaneously modulate its geometry and pore size from water to methanol and DMF in a reversible manner. The cage membrane exhibits ≥585.59 g mol-1 molecular weight cutoff preferentially in water and is impeded by methanol (799.8 g mol-1) and DMF (≈1017 g mol-1), reflecting 36 and 73% change in rejection due to self-regulation and the flexible network, respectively. Grazing incidence X-ray diffraction illustrates a clear peak downshift, suggesting an intrinsic structural change when the cage membranes were immersed in methanol or DMF. We have observed reversible structural changes that can also be tuned by preparing a methanol/DMF mixture and adjusting their ratio, thereby enabling gradient molecular filtration. We anticipate that such cage membranes with dynamic selectivity could be promising particularly for industrial separations and wastewater treatment.

A wear-resistant silicon nano-spherical AFM probe for robust nanotribological studies.

Nanoscale wear can severely limit the performance of tips used in atomic force microscopy, especially in contact and lateral mode operations. Hence, we investigated the mechanical and tribological properties of a newly invented nano-spherical silicon tip produced via swelling of single-crystal silicon using helium ion dosing to ascertain its reliability for AFM operations. The nanoindentation test proved that the modulus of elasticity of the nano-spheres tends to increase with the diameter of the spheres at 0.5 mN contact force. However, at 10 mN higher contact force, the elastic modulus was stable at ∼160 GPa irrespective of the sphere diameter. The SEM images confirmed the durability of the tip after 10 000 cycles of sliding on a silicon wafer and quartz surfaces. There was no damage on the tip and the wear debris was suggested to be from the localized wear on the counter wafer surface. Also, the in situ AFM pull-off force test indicated that the geometry of the tip remained unaltered during the wear test. The Si/SiO2 tribology study showed a decrease in coefficient of friction as velocity and sliding cycles increased which was attributed to the tribochemical reactions occurring at the Si/SiO2 interfaces. These results indicate that the new nano-spherical AFM tip has advantages in nanoscale tribology measurement.

Bio-Inspired Hierarchical Micro/Nanostructured Surfaces for Superhydrophobic and Anti-Ice Applications.

We report a scalable and cost-effective fabrication approach for constructing bio-inspired micro/nanostructured surfaces. It involves silicon microstructure etching using a deep reactive ion etch (DRIE) method, nanowires deposition via glancing angle deposition (GLAD) process, and fluorocarbon thin film deposition. Compared with the smooth, microstructured, and nanostructured surfaces, the hierarchical micro/nanostructured surfaces obtained via this method showed the highest water contact angle of ∼161° and a low sliding angle of <10°. It also offered long ice delay times of 2313 s and 1658 s at -5°C and -10°C respectively, more than 10 times longer than smooth surfaces indicating excellent anti-icing properties and offering promising applications in low-temperature environments. These analyses further proved that the surface structures have a significant influence on surface wettability and anti-icing behavior. Hence, the GLAD process which is versatile and cost-effective offers the freedom of constructing nanostructures on top of microstructures to achieve the required objective in the fabrication of micro/nanostructured surfaces when compared to other fabrication techniques.

Multilayer Reflective Coatings for BEUV Lithography: A Review.

The development of microelectronics is always driven by reducing transistor size and increasing integration, from the initial micron-scale to the current few nanometers. The photolithography technique for manufacturing the transistor needs to reduce the wavelength of the optical wave, from ultraviolet to the extreme ultraviolet radiation. One approach toward decreasing the working wavelength is using lithography based on beyond extreme ultraviolet radiation (BEUV) with a wavelength around 7 nm. The BEUV lithography relies on advanced reflective optics such as periodic multilayer film X-ray mirrors (PMMs). PMMs are artificial Bragg crystals having alternate layers of "light" and "heavy" materials. The periodicity of such a structure is relatively half of the working wavelength. Because a BEUV lithographical system contains at least 10 mirrors, the optics' reflectivity becomes a crucial point. The increasing of a single mirror's reflectivity by 10% will increase the system's overall throughput six-fold. In this work, the properties and development status of PMMs, particularly for BEUV lithography, were reviewed to gain a better understanding of their advantages and limitations. Emphasis was given to materials, design concepts, structure, deposition method, and optical characteristics of these coatings.

Formation of discrete periodic nanolayered coatings through tailoring of nanointerfaces-Toward zero macroscale wear.

Notwithstanding the success of nanolayered coatings in the reduction of wear at nano-/microscales, the improvement of the wear resistance at the macroscale remains an issue. Moreover, the effects of nanointerfaces in nanolayered coatings on their macrotribological properties are not understood well. This paper reports on the engineering of nanointerfaces in diamond-like C/Cr nanolayered coatings to tailor their characteristics including the degree of intermixing, defects, and Cr growth mode. The result was the fabrication of a coating with subnanometer-thick periodic albeit discrete Cr interlayers. This was achieved using our patented deposition technique. This coating contained less interfacial defects compared to classic nanolayered coatings with continuous nanolayers and presented record-breaking wear rates at the macroscale. Finite Element analysis was performed and micropatterning strategy was used to reduce the wear rate further. Last, we report on discovery of a dimensionless parameter that can be used to predict the wear resistance of carbon-based nanolayered coatings.

Hard, Flexible, and Transparent Nanolayered SiN x/BN Periodical Coatings.

In this study, SiN x/BN periodical nanolayered coatings (PNCs) are developed. PNCs were deposited at the room temperature on plastic and glass substrates. They demonstrate the excellent mechanical durability of inorganic materials and optical transparency and flexibility of organic ones. The 150 nm thick PNC shows optical transparency, sapphire-like hardness, high wear protection, and flexibility. Such a coating with a superior combination of optical and mechanical properties has not been reported previously.

Increased elasticity and damping capacity of diamond-like carbon coatings by immobilized C60 fullerene clusters.

Material loss and plastic deformation induced by frictional interactions at moving mechanical interfaces continue to be major issues responsible for efficiency and performance degradation of systems. Establishment of fully elastic interactions in the contact region without compromising the structural rigidity and integrity of materials represents a promising solution. In this study, we report on improving the elasticity, damping properties, ductility and wear resistance of diamond-like carbon (DLC) coatings through introducing an immobilized C60 cluster layer. The C60 clusters were immobilized using cysteamine (HS(CH2)2NH2) self-assembled monolayers (SAMs) attached to a pre-sputtered Au layer. A Ni adhesive layer was deposited onto plasma cleaned Si (100) substrates prior to Au, SAM-C60, and DLC deposition. Precise dynamic ultra nano-indentation tests indicated a drastic improvement in elasticity and damping capacity of the C60-DLC hybrid (Ni-Au-SAM/C60-DLC) multilayer coating compared to those of the C60-free (Ni-Au-DLC) multilayer. The behavior of the coatings under reciprocating contact conditions was evaluated. Quantification of the resistance of the coatings against wear and permanent deformation revealed a significant improvement in the wear rate from ∼3.38 × 10-8 to ∼5.14 × 10-10 mm3 N-1 mm-1 upon incorporation of the immobilized C60 clusters. The corresponding mechanisms were assessed through experiments and finite element (FE) simulations.

Highly durable and biocompatible periodical Si/DLC nanocomposite coatings.

Functional nanocomposite coatings comprised of periodically stacked nanolayers of diamond-like carbon (DLC) and amorphous silicon were developed for biomedical applications. The periodical nanocomposite structure provided high surface durability while silicon aided in reducing the residual stress. The structural, mechanical, tribological, and biomedical properties of the Si/DLC coatings deposited by magnetron sputtering were investigated systematically. The effect of the negative substrate bias on the structure and properties of the coatings was also assessed. The coatings demonstrated high durability and high biocompatibility. The bias voltage and bias mode affected both the hardness and residual stress of the Si/DLC coatings. Particularly, application of 60 V negative bias during the DLC layer deposition resulted in the lowest wear rate. FEM simulations showed that the wear resistance of the coatings was dictated by the hardness as well as the adhesion between the coatings and a chromium sub-layer. The periodical alternation of Si and DLC nanolayers led to a significant improvement of MC3T3 cell adhesion compared to the previously published data for Si-DLC composites.

Functional Multi-Nanolayer Coatings of Amorphous Carbon/Tungsten Carbide with Exceptional Mechanical Durability and Corrosion Resistance.

A novel functional multilayer coating with periodically stacked nanolayers of amorphous carbon (a:C)/tungsten carbide (WC) and an adhesion layer of chromium (Cr) was deposited on 304 stainless steel using a dual magnetron sputtering technique. Through process optimization, highly densified coatings with high elasticity and shear modulus, excellent wear resistance, and minimal susceptibility to corrosive and caustic media could be acquired. The structural and mechanical properties of the optimized coatings were studied in detail using a variety of analytical techniques. Furthermore, finite element method simulations indicated that the stress generated due to contact against a steel ball was distributed well within the coating, which allowed the stresses to be lower than the yield threshold of the coating. Thus, an ultralow wear rate of ∼10-12mm3/N mm could be achieved in dry sliding conditions under relatively high Hertzian contact pressures of ∼0.4-0.9 GPa. The amorphous and pinhole-free structure of the individual layers, sufficient number of pairs, and the relatively dense stacked layers resulted in significant polarization resistance (Z″ = 5.5 × 106 Ω cm2) and increased the corrosion resistance of the coating by 10-fold compared to that of recently reported corrosion-resistant coatings.

Highly wear-resistant and biocompatible carbon nanocomposite coatings for dental implants.

Diamond-like carbon coatings are increasingly used as wear-protective coatings for dental implants, artificial joints, etc. Despite their advantages, they may have several weak points such as high internal stress, poor adhesive properties or high sensitivity to ambient conditions. These weak points could be overcome in the case of a new carbon nanocomposite coating (CNC) deposited by using a C60 ion beam on a Co/Cr alloy. The structure of the coatings was investigated by Raman and XPS spectroscopy. The wear resistance was assessed by using a reciprocating tribotester under the loads up to 0.4 N in both dry and wet sliding conditions. Biocompatibility of the dental implants was tested in vivo on rabbits. Biocompatibility, bioactivity and mechanical durability of the CNC deposited on a Co/Cr alloy were investigated and compared with those of bulk Co/Cr and Ti alloys. The wear resistance of the CNC was found to be 250-650 fold higher compared to the Co/Cr and Ti alloys. Also, the CNC demonstrated much better biological properties with respect to formation of new tissues and absence of negative morphological parameters such as necrosis and demineralization. Development of the CNC is expected to aid in significant improvement of lifetime and quality of implants for dental applications.

Toward Zero Micro/Macro-Scale Wear Using Periodic Nano-Layered Coatings.

Wear is an important phenomenon that affects the efficiency and life of all moving machines. In this regard, extensive efforts have been devoted to achieve the lowest possible wear in sliding systems. With the advent of novel materials in recent years, technology is moving toward realization of zero wear. Here, we report on the development of new functional coatings comprising periodically stacked nanolayers of amorphous carbon and cobalt that are extremely wear resistant at the micro and macro scale. Because of their unique structure, these coatings simultaneously provide high elasticity and ultrahigh shear strength. As a result, almost zero wear was observed even after one million sliding cycles without any lubrication. The wear rate was reduced by 8-10-fold compared with the best previously reported data on extremely low wear materials.

Self-healing phenomenon and dynamic hardness of C60-based nanocomposite coatings.

The phenomenon of surface self-healing in C60-based polymer coatings deposited by ion-beam assisted physical vapor deposition was investigated. Nanoindentation of the coatings led to the formation of a protrusion rather than an indent. This protrusion was accompanied by an abnormal shape of the force-distance curve, where the unloading curve lies above the loading curve due to an additional force applied in pulling the indenter out of the media. The coatings exhibited a nanocomposite structure that was strongly affected by the ratio of C60 ion and C60 molecular beam intensities during deposition. The coatings also demonstrated the dynamic hardness effect, where the effective value of the hardness depends significantly on the indentation speed.

Effect of ion beam irradiation on the structure of ZnO films deposited by a dc arc plasmatron.

The deposition of polycrystalline ZnO film on a cold substrate was performed by using a plasmatron in rough vacuum condition. Low energy oxygen ion beam generated by a cold cathode ion source was introduced during the deposition process. The change of film property on the ion beam energy was checked. It is shown that irradiation by 200 eV ions improves crystalline structure of the film. Increasing of ion beam energy up to 400 eV leads to the degradation of a crystalline structure and decreases the deposition rate.