Enhancing Si3N4 Selectivity over SiO2 in Low-RF Power NF3-O2 Reactive Ion Etching: The Effect of NO Surface Reaction.

Highly selective etching of silicon nitride (Si3N4) and silicon dioxide (SiO2) has received considerable attention from the semiconductor community owing to its precise patterning and cost efficiency. We investigated the etching selectivity of Si3N4 and SiO2 in an NF3/O2 radio-frequency glow discharge. The etch rate linearly depended on the source and bias powers, whereas the etch selectivity was affected by the power and ratio of the gas mixture. We found that the selectivity can be controlled by lowering the power with a suitable gas ratio, which affects the surface reaction during the etching process. X-ray photoelectron spectroscopy of the Si3N4 and QMS measurements support the effect of surface reaction on the selectivity change by surface oxidation and nitrogen reduction with the increasing flow of O2. We suggest that the creation of SiOxNy bonds on the surface by NO oxidation is the key mechanism to change the etch selectivity of Si3N4 over SiO2.

Controllable Fabrication and Rectification of Bipolar Nanofluid Diodes in Funnel-Shaped Si3 N4 Nanopores.

Solid-state nanopores attract widespread interest, owning to outstanding robustness, extensive material availability, as well as capability for flexible manufacturing. Bioinspired solid-state nanopores further emerge as potential nanofluidic diodes for mimicking the rectification progress of unidirectional ionic transport in biological K+ channels. However, challenges that remain in rectification are over-reliance on complicated surface modifications and limited control accuracy in size and morphology. In this study, suspended Si3 N4 films of only 100 nm thickness are used as substrate and funnel-shaped nanopores are controllably etched on that with single-nanometer precision, by focused ion beam (FIB) equipped with a flexibly programmable ion dose at any position. A small diameter 7 nm nanopore can be accurately and efficiently fabricated in only 20 ms and verified by a self-designed mathematical model. Without additional modification, funnel-shaped Si3 N4 nanopores functioned as bipolar nanofluidic diodes achieve high rectification by simply filling each side with acidic and basic solution, respectively. Main factors are finely tuned experimentally and simulatively to enhance the controllability. Moreover, nanopore arrays are efficiently prepared to further improve rectification performance, which has great potential for high-throughput practical applications such as extended release of drugs, nanofluidic logic systems, and sensing for environmental monitoring and clinical diagnosis.

Osteocompatibility of Si3N4-coated carbon fiber-reinforced polyetheretherketone (CFRP) and hydroxyapatite-coated CFRP with antibiotics and antithrombotic drugs.

This study used a rabbit model to investigate the osteocompatibility of Si3N4-coated carbon fiber-reinforced polyetheretherketone (CFRP) and hydroxyapatite (HA)-coated CFRP with antibiotics (vancomycin [VCM]) and antithrombotic drugs (polyvinylpyrrolidone [PVP]). HA-coated cylindrical CFRP implants were used as the controls (HA), and HA-coated implants treated with VCM and PVP were prepared (HA-VP) as the test groups; a cylindrical CFRP coated with Si3N4 was also prepared (SiN). Ten implants from each group were randomly inserted into the femoral diaphysis of rabbits. The pull-out test, radiological analysis using micro-computed tomography (µ-CT), and histological analysis were performed. The pull-out strength of the SiN group was lower than that of the HA group. µ-CT analysis revealed that the amount of bone formation around the implant in the SiN group was inferior to that in the HA group. Conversely, the HA-VP group had equivalent pull-out strength and bone formation as analyzed by µ-CT compared to the HA group. In conclusion, the additional surface treatment of the HA-coated CFRP with VCM and PVP provided sufficient bone fixation and formation.

Operando photoelectron spectroscopy analysis of graphene field-effect transistors.

In this study, operando photoelectron spectroscopy was used to characterize the performance of graphene field-effect transistors under working conditions. By sweeping the back-gate voltages, the carrier concentration of the graphene channel on the 150 nm Si3N4/Si substrate was tuned. From the C1s core level spectra acquired under the application of different gate voltages, the binding energy shifts caused by electric-field effects were obtained and analyzed. Together with the C1s peak shape information and the photoluminescence spectrum of the Si3N4/Si substrate, the presence of local potential across the x-ray beam spot associated with defects and gate leakage current in amorphous Si3N4was identified. The presence of defects in Si3N4/Si substrate could not only screen the partial electric field generated by the back gate but also serve as long-range scattering centers to the carriers, thus affecting charge transport in the graphene channel. Our findings will help further investigate the dielectric/graphene interface properties and accelerate the utilization of graphene in real device applications.

Optimization of Silicon Nitride Waveguide Platform for On-Chip Virus Detection.

This work presents a rigorous and generic sensitivity analysis of silicon nitride on silicon dioxide strip waveguide for virus detection. In general, by functionalizing the waveguide surface with a specific antibodies layer, we make the optical sensor sensitive only to a particular virus. Unlike conventional virus detection methods such as polymerase chain reaction (PCR), integrated refractive index (RI) optical sensors offer cheap and mass-scale fabrication of compact devices for fast and straightforward detection with high sensitivity and selectivity. Our numerical analysis includes a wide range of wavelengths from visible to mid-infrared. We determined the strip waveguide's single-mode dimensions and the optimum dimensions that maximize the sensitivity to the virus layer attached to its surface at each wavelength using finite difference eigenmode (FDE) solver. We also compared the strip waveguide with the widely used slot waveguide. Our theoretical study shows that silicon nitride strip waveguide working at lower wavelengths is the optimum choice for virus detection as it maximizes both the waveguide sensitivity (Swg) and the figure of merit (FOM) of the sensor. The optimized waveguides are well suited for a range of viruses with different sizes and refractive indices. Balanced Mach-Zehnder interferometer (MZI) sensors were designed using FDE solver and photonic circuit simulator at different wavelengths. The designed sensors show high FOM at λ = 450 nm ranging from 500 RIU-1 up to 1231 RIU-1 with LMZI = 500 µm. Different MZI configurations were also studied and compared. Finally, edge coupling from the fiber to the sensor was designed, showing insertion loss (IL) at λ = 450 nm of 4.1 dB for the design with FOM = 500 RIU-1. The obtained coupling efficiencies are higher than recently proposed fiber couplers.

Stretchable and Compressible Si3 N4 Nanofiber Sponge with Aligned Microstructure for Highly Efficient Particulate Matter Filtration under High-Velocity Airflow.

Particulate matter (PM) is one of the most severe air pollutants and poses a threat to human health. Air filters with high filtration efficiency applied to the source of PM are an effective way to reduce pollution. However, many of the present filtration materials usually fail because of their high pressure drop under high-velocity airflow and poor thermal stability at high temperatures. Herein, a highly porous Si3 N4 nanofiber sponge (Si3 N4 NFS) assembled by aligned and well-interconnected Si3 N4 nanofibers is designed and fabricated via chemical vapor deposition (CVD). The resulting ultralight Si3 N4 NFS (2.69 mg cm-3 ) processes temperature-invariant reversible strechability (10% strain) and compressibility (50% strain), which enables its mechanical robustness under high-velocity airflow. The highly porous and aligned microstructure result in a Si3 N4 NFS with high filtration efficiency for PM2.5 (99.97%) and simultaneous low pressure drop (340 Pa, only <0.33% of atmospheric pressure) even under a high gas flow velocity (8.72 m s-1 ) at a high temperature (1000 °C). Furthermore, the Si3 N4 NFS air filter exhibits good long-term service ability and recyclability. Such Si3 N4 NFS with aligned microstructures for highly efficient gas filters provides new perspectives for the design and preparation of high-performance filtration materials.

All Si3 N4 Nanowires Membrane Based High-Performance Flexible Solid-State Asymmetric Supercapacitor.

Recently, much attention has been drawn in the development of flexible energy storage devices due to the increasing demands for flexible/portable electronic devices with high energy density, low weight, and good flexibility. Herein, vertically oriented graphene nanosheets (VGNs) are in situ fabricated on the surface of free-standing and flexible Si3 N4 nanowires (NWs) membrane by plasma-enhanced chemical vapor deposition (PECVD), which are directly used as flexible nanoscale conductive substrates. NiCo2 O4 hollow nanospheres (HSs) and FeOOH amorphous nanorods (NRs) are finally prepared on Si3 N4NWs @VGNs, which are served as the positive and negative electrodes, respectively. Profiting from the structural merits, the synthesized Si3 N4NWs @VGNs@NiCo2 O4HSs and Si3 N4NWs @VGNs@FeOOHNRs membrane electrodes exhibit remarkable electrochemical performance. Using Si3 N4NWs membrane as the separator, the assembled all Si3 N4NWs membrane-based flexible solid-state asymmetric supercapacitor (ASC) with a wide operating potential window of 1.8 V yields the outstanding energy density of 96.3 Wh kg-1 , excellent cycling performance (91.7% after 6000 cycles), and good mechanical flexibility. More importantly, this work provides a rational design strategy for the preparation of flexible electrode materials and broadens the applications of Si3 N4NWs in the field of energy storage.

Design and Simulation Investigation of Si3N4 Photonics Circuits for Wideband On-Chip Optical Gas Sensing around 2 µm Optical Wavelength.

We theoretically explore the potential of Si3N4 on SiO2 waveguide platform toward a wideband spectroscopic detection around the optical wavelength of 2 µm. The design of Si3N4 on SiO2 waveguide architectures consisting of a Si3N4 slot waveguide for a wideband on-chip spectroscopic sensing around 2 µm, and a Si3N4 multi-mode interferometer (MMI)-based coupler for light coupling from classical strip waveguide into the identified Si3N4 slot waveguides over a wide spectral range are investigated. We found that a Si3N4 on SiO2 slot waveguide structure can be designed for using as optical interaction part over a spectral range of interest, and the MMI structure can be used to enable broadband optical coupling from a strip to the slot waveguide for wideband multi-gas on-chip spectroscopic sensing. Reasons for the operating spectral range of the system are discussed.

In-Situ Synthesis and Characterization of Nanocomposites in the Si-Ti-N and Si-Ti-C Systems.

The pyrolysis (1000 °C) of a liquid poly(vinylmethyl-co-methyl)silazane modified by tetrakis(dimethylamido)titanium in flowing ammonia, nitrogen and argon followed by the annealing (1000-1800 °C) of as-pyrolyzed ceramic powders have been investigated in detail. We first provide a comprehensive mechanistic study of the polymer-to-ceramic conversion based on TG experiments coupled with in-situ mass spectrometry and ex-situ solid-state NMR and FTIR spectroscopies of both the chemically modified polymer and the pyrolysis intermediates. The pyrolysis leads to X-ray amorphous materials with chemical bonding and ceramic yields controlled by the nature of the atmosphere. Then, the structural evolution of the amorphous network of ammonia-, nitrogen- and argon-treated ceramics has been studied above 1000 °C under nitrogen and argon by X-ray diffraction and electron microscopy. HRTEM images coupled with XRD confirm the formation of nanocomposites after annealing at 1400 °C. Their unique nanostructural feature appears to be the result of both the molecular origin of the materials and the nature of the atmosphere used during pyrolysis. Samples are composed of an amorphous Si-based ceramic matrix in which TiNxCy nanocrystals (x + y = 1) are homogeneously formed "in situ" in the matrix during the process and evolve toward fully crystallized compounds as TiN/Si3N4, TiNxCy (x + y = 1)/SiC and TiC/SiC nanocomposites after annealing to 1800 °C as a function of the atmosphere.

Effect of Silicon Nitride/Oxide on the Structure and the Thermal Conductivity of CoSi Nanocomposites.

In this work, the fabrication of nanocomposites with silicon nitride/oxide into the thermoelectric matrix of cobalt silicide is presented. The different concentrations of nano-Si3N4 were intentionally introduced by mechanical grinding while it was found that the nanocomposites also included SiO2 phase at micro- as well as at nano-scale. The structural and morphological modifications of the materials were studied by powder X-ray Diffraction, Scanning Electron Microscopy and Transmission Electron Microscopy. The nanocomposites were studied in terms of Hall Effect, Seebeck coefficient, electrical and thermal conductivity. Emphasis is given on the lattice thermal conductivity that was analyzed based on Effective Medium Theory and the contribution of each phase is taken into account.

Preparation of 3D printed silicon nitride bioceramics by microwave sintering.

Silicon nitride (Si3N4) is a bioceramic material with potential applications. Customization and high reliability are the foundation for the widespread application of Si3N4 bioceramics. This study constructed a new microwave heating structure and successfully prepared 3D printed dense Si3N4 materials, overcoming the adverse effects of a large amount of 3D printed organic forming agents on degreasing and sintering processes, further improving the comprehensive performance of Si3N4 materials. Compared with control materials, the 3D printed Si3N4 materials by microwave sintering have the best mechanical performance: bending strength is 928 MPa, fracture toughness is 9.61 MPa·m1/2. Meanwhile, it has the best biocompatibility and antibacterial properties, and cells exhibit the best activity on the material surface. Research has shown that the excellent mechanical performance and biological activity of materials are mainly related to the high-quality degreasing, high cleanliness sintering environment, and high-quality liquid-phase sintering of materials in microwave environments.

Amorphous, Carbonated Calcium Phosphate and Biopolymer-Composite-Coated Si3N4/MWCNTs as Potential Novel Implant Materials.

A biodegradable amorphous carbonated calcium phosphate (caCP)-incorporated polycaprolactone (PCL) composite layer was successfully deposited by a spin coater. In this specific coating, the PCL acts as a bioadhesive, since it provides a better adherence of the coatings to the substrate compared to powder coatings. The caCP-PCL coatings were deposited and formed thin layers on the surface of a Si3N4-3 wt% MWCNT (multiwalled carbon nanotube) substrate, which is an emerging type of implant material in the biomedical field. The composite coatings were examined regarding their morphology, structure and biological performance. The biocompatibility of the samples was tested in vitro with MC3T3-E1 preosteoblast cells. Owing to the caCP-PCL thin layer, the cell viability values were considerably increased compared to the substrate material. The ALP and LDH tests showed numerous living cells on the investrigated coatings. The morphology of the MC3T3-E1 cells was examined by fluorescent staining (calcein and DAPI) and scanning electron microscopy, both of which revealed a well-spread, adhered and confluent monolayer of cells. All performed biocompatibility tests were positive and indicated the applicability of the deposited thin composite layers as possible candidates for orthopaedic implants for an extended period.

Parallel Grooved Microstructure Manufacturing on the Surface of Si3N4 Ceramics by Femtosecond Laser.

Machining special microstructures on the surface of silicon nitride ceramics helps improve their service performance. However, the high brittleness and low fracture toughness of silicon nitride ceramics make it extremely difficult to machine microstructures on their surface. In this study, a femtosecond laser is used to machine parallel grooved microstructures on the surface of silicon nitride ceramics. The effects of the laser polarization angle, laser single pulse energy, scanning line spacing, and laser scan numbers on the surface morphology and geometric characteristics of grooved microstructures are researched. It is found that a greater angle between the direction of the scanning path and laser polarization is helpful to obtain a smoother surface. As the single pulse energy increases, debris and irregular surface structures will emerge. Increasing the laser scan line spacing leads to clearer and more defined parallel grooved microstructures. The groove depth increases with the increase in the scan numbers. However, when a certain number of scans is reached, the depth will not increase further. This study serves as a valuable research foundation for the femtosecond laser processing of silicon nitride ceramic materials.

The impact of Si3N4 incorporation on the mechanical characteristics of ZrB2-SiC nanocomposite sintered via pressureless method.

Due to their unique properties, ultra-high-temperature ceramics possess have great potential for aerospace and industrial applications. In this study, we utilized ZrB2 and Si3N4 powders in micron scale, along with SiC powder in both nano and micron scale. A nanocomposite comprising ZrB2-20 vol% SiC (15 % nano - 5 % micron)-10 % ZrC was incorporated into the base composition by adding Si3N4 in volumes of 1-2-3 volume and 4 %. The process is carried out by pressure-less sintering at 2150 °C. The evaluation in this study involved X-ray diffraction (XRD) analysis, hardness measurement, density determination, fracture toughness assessment, and bending test. The results showed that addition of Si3N4 enhances the relative density, hardness, and fracture toughness of this nanocomposite. The sample with Si3N4volume fraction of 3 % has the best performance, with a relative density of 99.4 %, a hardness of 20.33 GPa, and a fracture toughness of 3.12 MPa M1/2.

A high-safety lithium-ion battery electrospun separator with Si3N4-assisted sulfonated poly(ether ether ketone) for regulating lithium flux.

The uncontrolled lithium (Li) dendrite growth significantly impacts the safety performance of polymer separators. To mitigate this growth, this study introduces Si3N4 into sulfonated poly(ether Ether Ketone) (SPEEK) and prepares Si3N4/SPEEK composite separators via electrospinning. At the interface between the Si3N4/SPEEK separator and the Li anode, the Si nanowires that form impede Li dendrite growth, thereby enhancing the electrochemical performance of lithium-ion batteries (LIBs). The Li deposition test of the 10 % Si3N4/SPEEK separator can operate for 1000 h without short-circuiting. Additionally, the LiFePO4||Li cell with the 10 % Si3N4/SPEEK separator shows improved initial discharge capacity (157.8 mAh g-1 at 1C) and superior rate performance (125 mAh g-1 at 10C). Moreover, the nano-scale Si3N4 endows the separator with robust thermal and mechanical properties. The FLIR observations reveal that the 10 % Si3N4/SPEEK separator maintains uniform thermal distribution and structural integrity even at 300 °C, ensuring safe battery operation at high temperatures. The additional load of the 10 % Si3N4/SPEEK separator can reach 10.2 mN, which enhances the puncture resistance of the separator. This work provides a solid approach for the application of SPEEK as a high-safety and high-rate LIB separator.

Production and characterization of low-density silicon nitride reinforced zinc nanocomposite coatings on mild steel for applications in marine and automotive industries.

In today's automotive, marine and petrochemical industries, the desire for lightweight materials has increased. Hence, necessitating the production of components with low density. In this work, lightweight Zn-Si3N4 coatings were developed by including Si3N4 in the zinc matrix. The optimal coatings were produced on steel samples at 45 °C and varied Si3N4 particles and voltages following ASTM A53/A53M standard. The deterioration (corrosion) property i.e. corrosion rate (CR) and current density (jocorr) of the uncoated (control) and coated samples were examined in 0.5 M of sulphuric acid using a potentiodynamic polarization technique following ASTM G3/G102 standard. The microstructure of the samples was studied via the SEM micrographs and XRD patterns, while the wear performance resistance (following ASTM G99 standard) and electrical conductivity of the samples were examined with a pin-on-disc tribometer and ammeter-voltmeter. The corrosion experiment indicated that the uncoated mild steel specimen possessed a CR of 12.345 mm year-1 and jocorr of 1060 µA/cm2, while the CR and jcorr of the coated samples ranged from 2.6793 to 4.7975 mm year-1 and 231-413 µA/cm2, respectively. The lower CR and jcorr values of the coated specimens, relative to the coated sample showed that the coatings possessed superior passivation ability in the test medium. The SEM micrographs of the samples showed refined morphology, while the XRD patterns revealed high peak intensity crystals such as Zn4SiN, ZnNSi, Zn4N and Zn2NSi, which could be beneficial to the mechanical properties and corrosion resistance of the steel. Moreover, the wear resistance study indicated that the COF of the uncoated sample ranged from 0.1 to 0.5, while those for coated specimens ranged from 0.05 to 0.35. Similarly, the uncoated steel exhibited a wear volume (WV) of 0.00508 mm3, while the WV of the coated specimens ranged from 0.00266 to 0.0028 mm3, indicating the existence of high strengthening mechanisms between the interface of the protecting device and the steel. Also, the electrical conductivity of the mild steel sample reduced from 12.97 Ω-1cm-1 to 0.64 Ω-1cm-1, indicating that the electrical resistivity of the steel was enhanced by the coatings.

Tailoring thermal transport and confinement effect of GaN/Si3N4nanowires utilizing core-shell architecture.

The thermal transport properties of nanowires (NWs) can be significantly influenced by the implementation of a core-shell structure, which introduces interface scattering and phonon localization effects, opening avenues for novel applications. In this paper, we use the method of non-equilibrium molecular dynamics to simulate the effects of system temperature, cross-sectional width, and nanopillar interface on the thermal transport of GaN/Si3N4core-shell NWs. The thermal transport process of phonons in core-shell NWs is studied by calculating the vibrational density of states, phonon participation rate, and dispersion curve. The results show that the core-shell NWs characterized by smooth interfaces exhibit a 17.4% decrease in thermal conductivity (TC) at room temperature when contrasted with pristine GaN NWs. Furthermore, the TC of GaN/Si3N4core-shell NWs can be further reduced by adding nanopillars at the interface. Due to resonance effect, thus effectively regulating the thermal transport. The presence of nanopillars increases phonon-surface scattering intensity at low-frequency and modifies phonon dispersion to decrease the group velocity. In addition, the hybridization of phonon modes between those of the nanopillars and the Si3N4shell gives rise to numerous dispersionless resonance phonon modes that span the entire phonon spectrum. This research delves into the effects of nanopillars and interfaces on thermal transport, providing important guidance for understanding confinement effects and establishing a robust theoretical basis for the regulation of thermal transport.

Investigation of the Effectiveness of Silicon Nitride as a Reinforcement Agent for Polyethylene Terephthalate Glycol in Material Extrusion 3D Printing.

Polyethylene terephthalate glycol (PETG) and silicon nitride (Si3N4) were combined to create five composite materials with Si3N4 loadings ranging from 2.0 wt.% to 10.0 wt.%. The goal was to improve the mechanical properties of PETG in material extrusion (MEX) additive manufacturing (AM) and assess the effectiveness of Si3N4 as a reinforcing agent for this particular polymer. The process began with the production of filaments, which were subsequently fed into a 3D printer to create various specimens. The specimens were manufactured according to international standards to ensure their suitability for various tests. The thermal, rheological, mechanical, electrical, and morphological properties of the prepared samples were evaluated. The mechanical performance investigations performed included tensile, flexural, Charpy impact, and microhardness tests. Scanning electron microscopy and energy-dispersive X-ray spectroscopy mapping were performed to investigate the structures and morphologies of the samples, respectively. Among all the composites tested, the PETG/6.0 wt.% Si3N4 showed the greatest improvement in mechanical properties (with a 24.5% increase in tensile strength compared to unfilled PETG polymer), indicating its potential for use in MEX 3D printing when enhanced mechanical performance is required from the PETG polymer.

Design of Superlubricity System Using Si3N4/Polyimide as the Friction Pair and Nematic Liquid Crystals as the Lubricant.

Polyimide (PI) is a high-performance engineering plastic used as a bearing material. A superlubricity system using Si3N4/PI as the friction pair and nematic liquid crystals (LCs) as the lubricant was designed. The superlubricity performance was studied by simulating the start-stop condition of the machine, and it was found that the superlubricity system had good reproducibility and stability. In the superlubricity system, friction aligned with the PI molecules, and this alignment was less relevant compared to which substance was rubbing on the PI. Oriented PI molecules induced LC molecule alignment when the pretilt angle was very small, and the LC molecules were almost parallel to the PI molecules due to the one-dimensional ordered arrangement of LC molecules and low viscosity, which is conducive to the occurrence of the superlubricity phenomenon.

The Effect of Intrinsic Mechanical Properties on Reducing the Friction-Induced Ripples of Hard-Filler-Modified HDPE.

Ripple deformations induced by friction on polymeric materials have negative effects on the entire stability of operating machineries. These deformations are formed as a response to contacting mechanics, caused by the intrinsic mechanical properties. High-density polyethylene (HDPE) with varying silicon nitride (Si3N4) contents is used to investigate different ripple deformation responses by conducting single-asperity scratch tests. The relationship between the intrinsic mechanical properties and the ripple deformations caused by filler modifications is analyzed in this paper. The results show the coupling of the inherent mechanical properties, and the stick-slip motion of HDPE creates ripple deformations during scratching. The addition of the Si3N4 filler changes the frictional response; the filler weakens the ripples and almost smoothens the scratch, particularly at 4 wt.%, but the continued increase in the Si3N4 content produces noticeable ripples and fluctuations. These notable differences can be attributed to the yield and post-yield responses; the high yield stress and strain-hardening at 4 wt.% provide good friction resistance and stress distribution, thus a smooth scratch is observed. In contrast, increasing the filler content weakens both the yield and post-yield responses, leading to deformation. The results herein reveal the mechanism behind the initial ripple deformation, thus providing fundamental insights into universally derived friction-induced ripples.