Silicon Atoms Research Articles

Reaction of a Disilyne with Internal Alkynes: Reversible [1 + 2] Cycloaddition and Formation of Strained Unsaturated Silacycles.

The reactions of NHB-stabilized disilyne (NHB)Si≡Si(NHB) (1, NHB = [ArN(CMe)2NAr]B, Ar = 2,6-iPr2C6H3) with internal alkynes were described. Reaction of disilyne 1 with one equivalent of bis(trimethylsilyl)acetylene led to a reversible [1 + 2] cycloaddition of one of the Si atoms with the alkyne and the insertion of the other Si into one of Ar rings with the formation of a silirenyl-silepin 2, whereas reaction of 1 with two equivalents of Me3SiCCSiMe3 resulted in the formal addition of the Csp-Si bond to the Si≡Si triple bond to give disilene (NHB)(Me3Si)Si=Si(CCSiMe3)(NHB). Reaction of 1 with 1,3-diyne Me3SiCCCCSiMe3 yielded a 1,2-disilacyclobut-3-ene via cycloaddition, ring expansion, and NHB 1,2-shift sequence. The initial [1 + 2] cycloaddition of one of the silicon atoms with an alkyne was strongly supported by DFT calculations. The results demonstrated the significant bis(silylene) character and rich synthetic potential of bis(boryl) disilyne 1.

Developments in the synthesis of allylsilanes by transition metal–catalyzed silylation of 1,3-dienes with disilanes

Abstract This highlight review overviews developments in the synthesis of allylsilanes by transition metal–catalyzed silylation of 1,3-dienes with disilanes. We specifically review disilylation, which installs 2 silicon atoms, and silyl-functionalization, which installs both silicon and another atom using disilanes and reagents such as nucleophiles and electrophiles. Utilizing these methods for the silylation of 1,3-dienes provides a robust protocol for the efficient synthesis of the desired allylsilanes in 1 step, thereby streamlining the silyl-functionalization of 1,3-dienes.

Synthesis of cyclic organosilicon compounds by palladium-catalyzed reactions of 2-silylaryl triflates

Abstract 2-Silylaryl triflates are widely employed as effective aryne precursors in organic synthesis, but their use as substrates for the synthesis of organosilicon compounds by retaining their silicon substituents is another attractive usage of these reagents. In particular, cyclic compounds with a silicon atom in the ring are promising candidates for various biologically active substances and optoelectronic functional materials. In this context, new synthetic methods for silicon-containing cyclic compounds have been actively investigated through the development of palladium-catalyzed reactions of 2-silylaryl triflates without generating aryne intermediates. As a result, selective synthesis of various silacyclic compounds has been achieved via C–H and/or C–Si bond activations as well as intramolecular exchange between these bonds and C–Pd bonds that are formed as reaction intermediates. An overview of this topic is described, including the mechanistic insights.

Cavity-enhanced single artificial atoms in silicon

Artificial atoms in solids are leading candidates for quantum networks, scalable quantum computing, and sensing, as they combine long-lived spins with mobile photonic qubits. Recently, silicon has emerged as a promising host material where artificial atoms with long spin coherence times and emission into the telecommunications band can be controllably fabricated. This field leverages the maturity of silicon photonics to embed artificial atoms into the world’s most advanced microelectronics and photonics platform. However, a current bottleneck is the naturally weak emission rate of these atoms, which can be addressed by coupling to an optical cavity. Here, we demonstrate cavity-enhanced single artificial atoms in silicon (G-centers) at telecommunication wavelengths. Our results show enhancement of their zero phonon line intensities along with highly pure single-photon emission, while their lifetime remains statistically unchanged. We suggest the possibility of two different existing types of G-centers, shedding new light on the properties of silicon emitters.

An optimizing study of silicon-based microchannels for enhanced thermal transfer

The thermal transport efficiency of microchannel heat sinks is critically influenced by the solid-liquid interface thermal resistance, an aspect that has historically been underappreciated in the design of these systems. We introduce a hybrid model that combines molecular dynamics simulations with computational fluid dynamics to rigorously investigate the interfacial heat transfer characteristics of microchannels. Our methodology involves constructing a nanochannel composed of silicon atoms and water molecules to accurately measure the thermal resistance at the Si–H2O interface. We then extend our analysis by developing two-dimensional rectangular microchannel models. These models are utilized to examine the effects of thermal resistance, channel dimensions, and inlet velocity on the overall interfacial heat transfer rate. Our findings indicate a pronounced size dependency in the variation of the total heat transfer rate, highlighting the critical role of scale in these systems. Significantly, enhancements in heat transfer efficiency are observed with an increase in inlet velocity and a reduction in thermal resistance. These results underscore the importance of optimizing both physical and operational parameters to enhance the efficiency of microchannel heat sinks. The findings are expected to inform future designs and promote more efficient thermal management solutions in various applications.

Physical mechanism underlying the enhancement effect of carbon in heavily phosphorus-doped Czochralski silicon substrate on phosphorus out-diffusion within n/n+ epitaxial wafer

The effects of carbon in heavily phosphorus-doped Czochralski (HP-Cz) silicon (Si) substrates, with the concentrations across an order of magnitude from 1016 to 1017 cm−3, on the out-diffusion of phosphorus impurities within n/n+ epitaxial Si (Epi-Si) wafers have been investigated. It is found that the increase in the carbon concentration ([C]) from 1.0 × 1016 to 1.0 × 1017 cm−3 leads to the enhanced phosphorus out-diffusion within the n/n+ Epi-Si wafer when subjected to anneal at 1100 °C in an N2 or an O2 ambient or to anneal at 1150 °C in an N2 ambient, but hardly affects the phosphorus out-diffusion within the n/n+ Epi-Si wafer when subjected to anneal at 1150 °C in an O2 ambient. Based on the density functional theory calculations, it is derived that the increase in the [C] from 1.0 × 1016 to 1.0 × 1017 cm−3 in the HP-Cz Si substrate results in a significantly increased thermal equilibrium concentration of self-interstitial silicon (SiI) atoms at 1100 or 1150 °C, which, in turn, leads to the increased concentration of the SiI atoms that out-diffuse from the substrate to the epitaxial layer because the SiI atoms diffuse extremely fast in Si. Such a carbon-induced increase in the concentration of SiI atoms is believed to be responsible for the aforementioned enhanced phosphorus out-diffusion, which is predominantly dictated by the interstitialcy mechanism. In the case of anneal in the O2 ambient at sufficiently high temperatures such as 1150 °C, a large number of excessive SiI atoms injected into the Epi-Si wafer substantially mask the carbon enhancement effect on the phosphorus out-diffusion. Of technological significance, it is deduced that the [C] should be not higher than 1.0 × 1016 cm−3 in the HP-Cz Si wafers as the substrates of n/n+ Epi-Si wafers used for power devices.

Regulating Ion Diffusion and Stability in Amorphous Thiosilicate‐Based Solid Electrolytes Through Edge‐Sharing Local Structures

AbstractAmorphous solid‐state electrolytes (SSEs) play a pivotal role as fundamental components within all‐solid‐state lithium batteries, yet their understanding lags behind that of crystalline materials. In this work, a novel amorphous SSE 5Li2S‐3SiS2 (mol %) with a high ionic conductivity of 1.2 mS cm−1 is first reported. The silicon and sulfur atoms in the edge‐sharing Si2S64− are less attracted to lithium compared to the SiS44− anion, which is expected to facilitate the lithium ions conduction in SSEs. More importantly, the relationship between the material properties and local structure in the amorphous thiosilicate SSEs is revealed, particularly highlighting the desirable edge‐sharing local structure. The Si2S64− presents better stability with Li metal. This work offers an important guideline in the development of anion frameworks in amorphous sulfide SSEs for high‐performance all‐solid‐state lithium metal batteries.

Reactor wall effects in Si–Cl2–Ar atomic layer etching

This work complements our previous manuscript [J. Vac. Sci. Technol. A41, 062602 (2023)] where predictions from molecular dynamics (MD) simulations of silicon–chlorine–argon (Si–Cl2–Ar) atomic layer etching (ALE) are compared to experiments. When etch product distributions for atomic chlorine (Cl) and silicon chlorides were initially compared to optical emission spectroscopy (OES) signals, it appeared that there was a discrepancy between the MD predictions and experimental results at higher ion fluences. Experiments showed a relatively long period of nearly constant Cl-containing etch products released from the ion-bombarded surface (referred to as the “plateau”) but this effect was not observed in MD simulations. In this report, we demonstrate that the “plateau” observed in the OES signals is most likely due to the desorption of Cl-containing etch products from the walls of the reactor and subsequent adsorption on the Si substrate. Experiments varying the gas residence time in the chamber while keeping incoming gas concentrations and pressure constant support this interpretation. We also conducted experiments with an additional Ar-only flow in the chamber to reduce the concentration of Cl-containing species on the chamber walls. For both sets of flow modification experiments, we observe results consistent with the hypothesis that Cl-containing species desorbing from chamber walls are a significant cause of the observed discrepancy between MD predictions and experimental observations. If the measured OES signals are corrected for this “additional” source of Cl-containing species at the surface, the MD predictions and measured OES signals are in excellent agreement. This further supports the predictive capability of MD simulations to accurately capture the relevant physical and chemical processes in plasma-assisted ALE processes. We provide an order of magnitude estimate of the required density of Cl-containing species that would account for the additional etch products observed. Finally, we discuss the implications of this effect on ALE in plasma nanofabrication.

Silicene/BN heterostructure as high-performance anode material for Mg-ion batteries

Finding a suitable anode material is a key part of the development of Mg-ion batteries (MIBs) to commercialize. In this work, an outstanding Silicene/BN heterostructure was discovered as a candidate anode material for MIBs by using first-principles calculations. The mixed sp2/sp3 orbital hybridization of silicon atoms makes Silicene monolayer easy to adsorb Mg atoms. The introduction of BN monolayer can effectively buffer the structural deformation and improve the electrochemical performances. Compared to pristine Silicene, the Silicene/BN heterostructure exhibited higher structural stability and Mg adsorption capacity. The diffusion of Mg ions in the heterostructure interlayer was easier with a low barrier of 0.160 eV than that on the Silicene monolayer. A comparable low open circuit voltage (0.112 V) was also observed. These results indicated the potential of Silicene/BN heterostructure as a high-performance anode material for MIBs.

Co contamination of Si: Plating & aging

Cobalt has emerged as a vital material in 10 nm technology for localized interconnect layers, potentially offering a compelling alternative to Cu-based interconnects. In this study, we subjected the contamination arising from the presence of cobalt atoms in silicon to comprehensive investigation, employing electron transmission electron microscopy (TEM) observations in conjunction with first-principles calculations. The results show that a dense CoSi layer with a thickness of a few nanometers is formed at the interface of cobalt and Si. The CoSi layer blocks the diffusion of Co atoms into Si. This is due to the semiconducting nature of the covalent bond formed between Co and Si, leading to the emergence of a forbidden zone at the Co/CoSi interface. The diffusion of Co into CoSi is governed by the atomic exchange mechanism, however, the local distortion of the periodic atomic potential due to the presence of the forbidden zone at the Co/CoSi interface hinders the diffusion of Co into Si. Therefore, the deposition of a Co metal layer on a Si chip does not require an additional barrier layer.

THE EXPERIENCE OF USING A NEW PHARMACOLOGICALLY ACTIVE COMPOSITION OF NANOSTRUCTURED FLUORAPATITE IN THE TREATMENT OF EARLY MANIFESTATIONS OF INCREASED TOOTH ABRASION

Despite the obvious successes in the field of preventive and conservative dentistry, the prevalence of abrasion of teeth (ITP) continues to grow: during the period 1992-2004, the proportion of diseases of hard tissues of teeth with elimination properties increased from 30.9 ± 1.8% to 38.2 ± 1.3%, i.e. increased by 7.3% [1, 7-10]. Many issues related to the diagnosis and planning of an integrated approach to the provision of dental care to patients with moderate CAH have not yet been sufficiently studied and covered [2]. Biologically active calcium phosphate in gel or colloidal state is currently of increasing interest in many areas of clinical medicine related to the problem of regeneration of soft and hard tissues of the body. It has been established that the biological activity of apatite largely depends on the size of its particles or grains, and the higher the dispersion of the substance, the more pronounced it is [3]. The use of pure compounds, as well as various combinations of bioactive substances to improve properties such as adhesion, bioactivity and biocompatibility, is also very promising [4]. A promising direction of modification of calcium hydroxyapatite (HCA) from the point of view of obtaining materials with improved properties is the introduction of fluorine and silicon atoms into the structure of HCA. This transformation increases the stability of the material in the chemically active environment of the human body (due to the presence of fluoride ions) and increases its biological activity (due to the presence of silicate ions), while maintaining the inherent biocompatibility of HAP [5]. Nanotechnology is used in the study, production and use of nanostructures, devices and systems, including targeted control and modification of the shape, size, interaction and integration of their constituent nanoscale elements (1-100 nm) to obtain objects with new chemical, physical and biological properties. A number of technologies and methods. Direct transport of medicines to the focus of the pathological process can increase the effectiveness of existing drug therapies [6]. A promising direction in modern dentistry is the creation of new pharmacological agents with particle sizes of the order of 10-9 (nanoparticles) for noninvasive treatment and early prevention of dental diseases. The aim of the study was to study the effectiveness of new pharmacologically active compositions of nanostructured fluorohydroxyapatite in the treatment of early symptoms of dental hyperextension.

The Elemental Composition Investigation of Silicon Doped with Gallium and Antimony Atoms

This work is devoted to the development of a diffusion technology for creating gallium antimonide (GaSb)-type complexes in the silicon crystal lattice as well as to the study of the electrical characteristics of the resulting layers. Based on the X-ray spectral analysis of the microcrystals formed on a silicon sample surface that was simultaneously doped with gallium and antimony atoms, it was demonstrated that the sample surface layer contains microcrystals having silicon, gallium, and antimony atoms. This allowed to admit a possibility of the oriented growth of crystals of the composition (GaSb)0.8Si0.2 on the silicon surface. A substantial impact of the processes of the complex formation that occured at high concentrations of ions of diffusing impurities on the distribution profile of charge carriers is demonstrated. Materials containing GaSb-type complexes in the bulk of the silicon lattice can be produced using ion doping, simultaneous diffusion, or epitaxy processes.

Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines.

The low-electron count, air-stable, platinum complexes [Pt(ItBu')(ItBu)][BArF] (C1) (ItBu=1,3-di-tert-butylimidazol-2-ylidene), [Pt(SiPh)3(ItBuiPr)2][BArF] (C2) (ItBuiPr=1-tert-butyl-3-iso-propylimidazol-2-ylidene), [Pt(SiPh)3(ItBuMe)2][BArF] (C3), [Pt(GePh3)(ItBuiPr)2][BArF] (C4), [Pt(GePh)3(ItBuMe)2][BArF] (C5) and [Pt(GeEt)3(ItBuMe)2][BArF] (C6) (ItBuMe=1-tert-butyl-3-methylimidazol-2-ylidene) are efficient catalysts (particularly the germyl derivatives) in both the silylative dehydrocoupling and hydrosilylation of electron rich alkenes derived from enamines. The steric hindrance exerted by the NHC ligand plays an important role in the selectivity of the reaction. Thus, bulky ligands are selective towards the silylative dehydrocoupling process whereas less sterically hindered promote the selective hydrosilylation reaction. The latter is, in addition, regioselective towards the β-carbon atom of both internal and terminal enamines, leading to β-aminosilanes. Moreover, the syn stereochemistry of the amino and silyl groups implies an anti Si-H bond addition across the double bond. All these facts point to a mechanistic picture that, according to experimental and computational studies, involves a non-classical hydrosilylation process through an outer-sphere mechanism in which a formal nucleophilic addition of the enamine to the silicon atom of a platinum σ-SiH complex is the key step. This is in sharp contrast with the classical Chalk-Harrod mechanism prevalent in platinum chemistry.

Electrophilic Hydrosilylation of Electron‐Rich Alkenes Derived from Enamines

AbstractThe low‐electron count, air‐stable, platinum complexes [Pt(ItBu’)(ItBu)][BArF] (C1) (ItBu=1,3‐di‐tert‐butylimidazol‐2‐ylidene), [Pt(SiPh)3(ItBuiPr)2][BArF] (C2) (ItBuiPr=1‐tert‐butyl‐3‐iso‐propylimidazol‐2‐ylidene), [Pt(SiPh)3(ItBuMe)2][BArF] (C3), [Pt(GePh3)(ItBuiPr)2][BArF] (C4), [Pt(GePh)3(ItBuMe)2][BArF] (C5) and [Pt(GeEt)3(ItBuMe)2][BArF] (C6) (ItBuMe=1‐tert‐butyl‐3‐methylimidazol‐2‐ylidene) are efficient catalysts (particularly the germyl derivatives) in both the silylative dehydrocoupling and hydrosilylation of electron rich alkenes derived from enamines. The steric hindrance exerted by the NHC ligand plays an important role in the selectivity of the reaction. Thus, bulky ligands are selective towards the silylative dehydrocoupling process whereas less sterically hindered promote the selective hydrosilylation reaction. The latter is, in addition, regioselective towards the β‐carbon atom of both internal and terminal enamines, leading to β‐aminosilanes. Moreover, the syn stereochemistry of the amino and silyl groups implies an anti Si−H bond addition across the double bond. All these facts point to a mechanistic picture that, according to experimental and computational studies, involves a non‐classical hydrosilylation process through an outer‐sphere mechanism in which a formal nucleophilic addition of the enamine to the silicon atom of a platinum σ‐SiH complex is the key step. This is in sharp contrast with the classical Chalk–Harrod mechanism prevalent in platinum chemistry.

Nanometer – Thick titanium film as a silicon migration barrier

Diffusion of silicon atoms to the topmost film surface poses significant challenges in various technological applications. In an effort to address this issue, titanium films with varying thicknesses were deposited on a silicon substrate to evaluate the efficacy of a thin titanium barrier film in blocking silicon migration to the upper film surface. Subsequently, the films were subjected to a 1-hour heating process in air at an oxidizing temperature of 430 K. Atomic force microscopy and Raman spectroscopy were employed to characterize the morphological and structural changes among the investigated films. X-ray photoelectron spectroscopy was utilized to explore variations in chemical composition, determine oxidation states, and measure the thicknesses of the thin titanium oxide layers. The findings revealed that titanium films with a thickness < 50 nm experienced silicon diffusion to their upper film surface. Moreover, an increase in the thickness of the oxide layers over the titanium film on the silicon substrate significantly reduced the migration of silicon to the titanium film surface. At 430 K, the study found that oxide layers at least 6.87 nm thick formed on a 35-nm thick titanium layer, which together successfully prevented silicon migration to the top surface of the film.

Large-capacity adsorption of the organic dye with surface-silanol-rich hybrid nano silica

Surface-silanol-rich hybrid nano silica was synthesized with a reverse-phase microemulsion method. Exposure ratio of the surface silicon atom reached 81.4 % with the mildest drying method of air-drying at room temperature, which enabled a large amount of amino (5.8 mmol g−1) and silanol (8.0 mmol g−1) to be simultaneously generated on the surface. Abundant surface groups enabled the present material to efficiently remove various anionic dyes from the wastewater with a maximum adsorption capacity of 2048 mg g−1. The reported result supplied good reference for the designing of the adsorbent through modulating the surface groups’ composition and amount.

Generation and Identification of the Trifluorosilylarsinidene F3SiAs and Isomeric Perfluorinated Arsasilene FAsSiF2.

The trifluorosilylarsinidene F3SiAs in the triplet ground state has been generated through the reaction of laser-ablated silicon atoms with AsF3 in cryogenic Ne- and Ar-matrices. The reactions proceed with the initial formation of perfluorinated arsasilene FAsSiF2 in the singlet ground state by two As-F bonds insertion reaction on annealing. The trifluorosilylarsinidene F3SiAs was formed via F-migration reactions of FAsSiF2 under irradiation at UV light (λ = 275 nm). The characterization of FAsSiF2 and F3SiAs by IR matrix-isolation spectroscopy is supported by computations at CCSD(T)-F12/aug-cc-pVTZ and B3LYP/aug-cc-pVTZ levels of theory.

Wear-resistant and adherent nanodiamond composite thin film for durable and sustainable silicon carbide mechanical seals

In response to environmental concerns, there is a growing demand for durable and sustainable mechanical seals, particularly in high-risk industries like chemical, petroleum, and nuclear sectors. This work proposes augmenting the durability and sustainability of silicon carbide (SiC) ceramic seals with the application of a nanodiamond composite (NDC) film through coaxial arc plasma deposition (CAPD) in a vacuum atmosphere. The NDC coating, with a smooth surface roughness of Ra = 60 nm as substrate, demonstrated a thickness of 1.1 μm at a deposition rate of 2.6 μm/h. NDC film has demonstrated exceptional mechanical and tribological characteristics, such as a hardness (H) of 48.5 GPa, Young's modulus (E) of 496.7 GPa, plasticity index (H/E) of 0.098, and fracture toughness of H3/E2 = 0.46 GPa, respectively. These NDC films showcased commendable adhesion strength (>60 N), negligible wear, and low friction (≤0.18) during dry sliding against a SiC counter material. Raman analysis has confirmed the nanocomposite structure of NDC film, emphasizing the role of highly energetic carbon ions in enhancing film adhesion by forming SiC intermetallic compounds at the interface through the diffusion of silicon atoms from the substrate into the films. The abundance of grain boundaries and rehybridization of carbon sp3 to sp2 bonding is perceived to improve tribological performance. CAPD excels in synthesizing long-life eco-friendly NDC coatings for durable and sustainable mechanical seals, featuring smooth surfaces, superior adhesion, outstanding hardness, and wear resistance, making them high potential candidates for various tribological applications.

Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation.

The catalytic access of silicon-stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization of the symmetric precursors with two identical substitutes attached to silicon atom. Here we report the construction of silicon-stereogenic organosilanes via catalytic kinetic resolution of racemic monohydrosilanes with good to excellent selectivity factors. Both Si-stereogenic dihydrobenzosiloles and Si-stereogenic monohydrosilanes could be efficiently accessed in one single operation via Rh-catalyzed enantioselective intramolecular hydrosilylation, employing (R,R)-Et-DuPhos as the optimal ligand. This catalytic protocol features mild conditions, a low catalyst loading (0.1 mol % [Rh(cod)Cl]2), high stereoinduction (S factor up to 152), and excellent scalability. Moreover, further derivatizations led to the efficient synthesis of uncommon middle-size (7- and 8-membered) Si-stereogenic silacycles. Preliminary mechanistic study indicates this reaction might undergo a modified Chalk-Harrod mechanism.

Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation

AbstractThe catalytic access of silicon‐stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization of the symmetric precursors with two identical substitutes attached to silicon atom. Here we report the construction of silicon‐stereogenic organosilanes via catalytic kinetic resolution of racemic monohydrosilanes with good to excellent selectivity factors. Both Si‐stereogenic dihydrobenzosiloles and Si‐stereogenic monohydrosilanes could be efficiently accessed in one single operation via Rh‐catalyzed enantioselective intramolecular hydrosilylation, employing (R,R)‐Et‐DuPhos as the optimal ligand. This catalytic protocol features mild conditions, a low catalyst loading (0.1 mol % [Rh(cod)Cl]2), high stereoinduction (S factor up to 152), and excellent scalability. Moreover, further derivatizations led to the efficient synthesis of uncommon middle‐size (7‐ and 8‐membered) Si‐stereogenic silacycles. Preliminary mechanistic study indicates this reaction might undergo a modified Chalk–Harrod mechanism.