Search Results (12)

Silicon oxycarbide coatings are the subject of research due to their exceptional optical, electronic, anti-corrosion, etc., properties, which make them attractive for a number of applications. In this article, we present a study on the synthesis and characterization of thin SiOC:H silicon oxycarbide films with the given composition and properties from a new organosilicon precursor octamethyl-1,4-dioxatetrasilacyclohexane (²D₂) and its macromolecular equivalent—poly(oxybisdimethylsily1ene) (POBDMS). Layers from ²D₂ precursor with different SiOC:H structure, from polymeric to ceramic-like, were produced in the remote microwave hydrogen plasma by CVD method (RHP-CVD) on a heated substrate in the temperature range of 30–400 °C. SiOC:H polymer layers from POEDMS were deposited from solution by spin coating and then crosslinked in RHP via the breaking of the Si-Si silyl bonds initiated by hydrogen radicals. The properties of SiOC:H layers obtained by both methods were compared. The density of the cross-linked materials was determined by the gravimetric method, elemental composition by means of XPS, chemical structure by FTIR spectroscopy, and NMR spectroscopy (¹³C, ²⁹Si). Photoluminescence analyses and ellipsometric measurements were also performed. Surface morphology was characterized by AFM. Based on the obtained results, a mechanism of initiation, growth, and cross-linking of the CVD layers under the influence of hydrogen radicals was proposed. Full article

Significant progress has been made in recent years in the use of atmospheric pressure plasma techniques for surface modification. This research focused on the beneficial effects of these processes on natural by-products, specifically those involving natural fiber-based materials. The study explored the deposition of hydrophobic organosilicon-like thin films onto flax fibres through plasma-enhanced chemical vapour deposition (PECVD), using tetramethylcyclotetrasiloxane (TMCTS) as the precursor. After the successful deposition of hydrophobic organosilicon-like thin films onto the flax fibres, polylactic acid (PLA) composite materials were fabricated. This fabrication process sets the stage for an in-depth analysis of the modified materials. Subsequently, these flax fabrics were subjected to meticulous characterization through scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. The results demonstrated successful TMCTS deposition on the surface which led to a complete hydrophobization of the flax fibers. Mechanical tests of the PLA/flax fibre composites revealed a significant improvement in load transfer and interfacial compatibility following the surface modification of the flax fibres. This improvement was attributed to the enhanced adhesion between the modified fibres and the PLA matrix. The findings highlight the potential of TMCTS-based PECVD as a practical surface modification technique, effectively enhancing the mechanical properties of PLA/flax fibre composites. These developments open exciting possibilities for sustainable and high-performance composite materials in various industries. Full article

Plasma polymerized (PP) thin films deposited in a soft or intermediate plasma discharge from hexamethyldisiloxane (HMDSO) were developed as sensors for the detection of volatile organic compound (VOC) vapors. Energy dispersive X-ray spectroscopy (EDX) and X-ray reflectometry (XRR) were performed to determine the organosilicon films’ elemental composition and density. Spectroscopic ellipsometry measurements were carried out to determine the refractive index of the films. Quartz crystal microbalance (QCM) and ellipsometry coupled to vapor sorption were used to investigate the sorption mechanism of several VOC vapors into the films as a function of the plasma deposition conditions. The density and the refractive index of the PP-HMDSO films increased with the plasma energy due to a different chemical composition and different proportion of free volumes in the material network. The PP-HMDSO films showed different affinities towards the VOC vapors depending on the plasma discharge energy. The films elaborated in the lowest plasma energy revealed a good sensitivity towards the VOCs, especially toluene (one of the BTEX vapors), compared to the other films deposited under higher plasma energy. In addition, the selectivity between toluene and other non-BTEX VOCs such as heptane and ethanol decreased to become zero while increasing the plasma energy. Full article

Titanium dioxide has attracted a great deal of attention in the field of environmental purification due to its photocatalytic activity under ultraviolet light. Photocatalytic efficiency and the energy required to initiate the process remain the drawbacks that hinder the widespread adoption of the process. Consistently with this, it is proposed here the polymerization of hexamethyldisiloxane fragments simultaneously to TiO₂ sputtering for the production of thin films in low-pressure plasma. The effect of plasma excitation power on the molecular structure and chemical composition of the films was evaluated by infrared spectroscopy. Wettability and surface energy were assessed by a sessile drop technique, using deionized water and diiodomethane. The morphology and elemental composition of the films were determined using scanning electron microscopy and energy dispersive spectroscopy, respectively. The thickness and roughness of the resulting films were measured using profilometry. Organosilicon-to-silica films, with different properties, were deposited by combining both deposition processes. Titanium was detected from the structures fabricated by the hybrid method. It has been observed that the proportion of titanium and particles incorporated into silicon-based matrices depends on the plasma excitation power. In general, a decrease in film thickness with increasing power has been observed. The presence of Ti in the plasma atmosphere alters the plasma deposition mechanism, affecting film deposition rate, roughness, and wettability. An interpretation of the excitation power dependence on the plasma activation level and sputtering yield is proposed. The methodology developed here will encourage researchers to create TiO₂ films on a range of substrates for their prospective use as sensor electrodes, water and air purification systems, and biocompatible materials. Full article

We report an investigation into 1,4-Bis-N,N-(trimethylsilyl)piperazine (BTMSP) as a novel precursor for the synthesis of silicon carbonitride films by chemical vapor deposition (CVD). The thermal stability, temperature dependence of vapor pressure and thermodynamic constants of the evaporation process of BTMSP were determined by static tensimetry with a glass membrane zero manometer. The transformation of the compound in low-power (25 W) plasma conditions was investigated by optical emission spectroscopy. It was shown that BTMSP undergoes destruction, accompanied by H and CH elimination and CN formation. SiCN(H) films were deposited in a hot-wall plasma-enhanced CVD reactor. The optical properties of the films were studied by spectral ellipsometry (refractive index: 1.5–2.2; absorption coefficient: 0–0.12) and UV–Vis spectroscopy (transmittance: up to 95%; optical bandgap: 1.6–4.9 eV). Information on the aging behavior of the films is also provided. The transformation of the films occurred through water adsorption and the formation of Si–O bonds with the degradation of Si–H, N–H and Si–CH_x–Si bonds. Full article

Stoichiometric silicon carbide (SiC) thin films were grown using thermal chemical vapor deposition (TCVD) from the single source precursor 1,3,5-trisilacyclohexane (TSCH) on c-Si (100) substrates within an optimized substrate temperature window ranging from 650 to 850 °C. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analyses revealed that the as-deposited films consisted of a Si-C matrix with a Si:C ratio of ~1:1. FTIR and photoluminescence (PL) spectrometry studies showed that films deposited ≥ 750 °C were defect- and H-free within the detection limit of the techniques used, while ellipsometry measurements yielded an as-grown SiC average refractive index of ~2.7, consistent with the reference value for the 3C-SiC phase. The exceptional quality of the films appears sufficient to overcome limitations associated with structural defects ranging from failure in high voltage, high temperature electronics to 2-D film growth. TSCH, a liquid at room temperature with good structural stability during transport and handling as well as high vapor pressure (~10 torr at 25 °C), provides a viable single source precursor for the growth of stoichiometric SiC without the need for post-deposition thermal treatment. Full article

The deposition rates of protective coatings resembling polydimethylsiloxane (PDMS) were measured with numerous sensors placed at different positions on the walls of a plasma-enhanced chemical vapor deposition (PECVD) reactor with a volume of approximately 5 m³. The plasma was maintained by an asymmetric capacitively coupled radiofrequency (RF) discharge using a generator with a frequency 40 kHz and an adjustable power of up to 8 kW. Hexamethyldisiloxane (HMDSO) was leaked into the reactor at 130 sccm with continuous pumping using roots pumps with a nominal pumping speed of 8800 m³ h⁻¹ backed by rotary pumps with a nominal pumping speed of 1260 m³ h⁻¹. Deposition rates were measured versus the discharge power in an empty reactor and a reactor loaded with samples. The highest deposition rate of approximately 15 nm min^–1 was observed in an empty reactor close to the powered electrodes and the lowest of approximately 1 nm min^–1 was observed close to the precursor inlet. The deposition rate was about an order of magnitude lower if the reactor was fully loaded with the samples, and the ratio between deposition rates in an empty reactor and loaded reactor was the largest far from the powered electrodes. The results were explained by the loss of plasma radicals on the surfaces of the materials facing the plasma and by the peculiarities of the gas-phase reactions typical for asymmetric RF discharges. Full article

Since the application of silicon materials in electronic devices in the 1950s, microprocessors are continuously getting smaller, faster, smarter, and larger in data storage capacity. One important factor that makes progress possible is decreasing the dielectric constant of the insulating layer within the integrated circuit (IC). Nevertheless, the evolution of interlayer dielectrics (ILDs) is not driven by a single factor. At first, the objective was to reduce the dielectric constant (k). Reduction of the dielectric constant of a material can be accomplished by selecting chemical bonds with low polarizability and introducing porosity. Moving from silicon dioxide, silsesquioxane-based materials, and silica-based materials to porous silica materials, the industry has been able to reduce the ILDs’ dielectric constant from 4.5 to as low as 1.5. However, porous ILDs are mechanically weak, thermally unstable, and poorly compatible with other materials, which gives them the tendency to absorb chemicals, moisture, etc. All these features create many challenges for the integration of IC during the dual-damascene process, with plasma-induced damage (PID) being the most devastating one. Since the discovery of porous materials, the industry has shifted its focus from decreasing ILDs’ dielectric constant to overcoming these integration challenges. More supplementary precursors (such as Si–C–Si structured compounds), deposition processes (such as NH₃ plasma treatment), and post porosity plasma protection treatment (P4) were invented to solve integration-related challenges. Herein, we present the evolution of interlayer dielectric materials driven by the following three aspects, classification of dielectric materials, deposition methods, and key issues encountered and solved during the integration phase. We aim to provide a brief overview of the development of low-k dielectric materials over the past few decades. Full article

In this work, optical coatings with a gradient of the refractive index are described. Its aim was to deposit, using the RF PECVD method, films of variable composition (ranging from silicon carbon-oxide to silicon carbon-nitride) for a smooth change of their optical properties enabling a production of the filter with a refractive index gradient. For that purpose, two organosilicon compounds, namely tetramethyldisilazane and hexamethyldisilazane, were selected as precursor compounds. The results reveal better optical properties of the materials obtained from the latter source. Depending on whether deposited in pure oxygen atmosphere or under conditions of pure nitrogen, the refractive index of the coatings amounted to 1.65 and to 2.22, respectively. By using a variable composition N₂/O₂ gas mixture, coatings of intermediate magnitudes of “n” were acquired. The optical properties were investigated using both UV-Vis absorption spectroscopy and variable angle spectroscopic ellipsometry. The chemical structure of the coatings was studied with the help of Fourier transform infrared and X-ray photoelectron spectroscopies. Finally, atomic force microscopy was applied to examine their surface topography. As the last step, a “cold mirror” type interference filter with a gradient of refractive index was designed and manufactured. Full article

Thin film deposition with atmospheric pressure plasmas is highly interesting for industrial demands and scientific interests in the field of biomaterials. However, the engineering of high-quality films by high-pressure plasmas with precise control over morphology and surface chemistry still poses a challenge. The two types of atmospheric-pressure plasma depositions of organosilicon films by the direct and indirect injection of hexamethyldisiloxane (HMDSO) precursor into a plasma region were chosen and compared in terms of the films chemical composition and morphology to address this. Although different methods of plasma excitation were used, the deposition of inorganic films with above 98% of SiO₂ content was achieved for both cases. The chemical structure of the films was insignificantly dependent on the substrate type. The deposition in the afterglow of the DC discharge resulted in a soft film with high roughness, whereas RF plasma deposition led to a smoother film. In the case of the RF plasma deposition on polymeric materials resulted in films with delamination and cracks formation. Lastly, despite some material limitations, both deposition methods demonstrated significant potential for SiO_x thin-films preparation for a variety of bio-related substrates, including glass, ceramics, metals, and polymers. Full article

In this study, pairs of the organosilicon/silicon oxynitride (SiO_xN_y) barrier structures with an ultralow water vapor transmittance rate (WVTR) were consecutively prepared by the plasma-enhanced chemical vapor deposition at a low temperature of 70 °C using the tetramethylsilane (TMS) monomer and the TMS-oxygen-ammonia gas mixture, respectively. The thickness of the SiO_xN_y film in the barrier structure was firstly designed by optimizing its effective permeability. The WVTR was further decreased by inserting an adequate thickness of the organosilicon layer as the stress residing in the barrier structure was released accordingly. By prolonging the diffusion pathway for water vapor permeation, three-paired organosilicon/SiO_xN_y multilayered barrier structure with a WVTR of about 10⁻⁵ g/m²/day was achievable for meeting the requirement of the thin film encapsulation on the organic light emitting diode. Full article

The possibility of controlling the density of organosilicon films was investigated by tuning the plasma activation degree without providing extra energy to the structure, as usually reported in the literature. For this purpose, thin films were deposited in plasmas fed with hexamethyldisiloxane/Ar mixtures at a total pressure of 9.5 Pa. The power of the radiofrequency excitation signal, P, ranged from 50 to 300 W to alter the average energy of the plasma species while the electrical configuration was chosen to avoid direct ion bombardment of the growing films. In this way, it was possible to evaluate the effect of P on the film properties. Thickness and deposition rate were derived from profilometry data. X-ray energy dispersive and infrared spectroscopies were, respectively, applied to analyze the chemical composition and molecular structure of the layers. Surface topography and roughness were determined by atomic force microscopy while nanoindentation was used to evaluate the mechanical properties of the films. From electrochemical impedance spectroscopy the total resistance to the flow of electrolyte species was derived. The main alteration observed in the structure with changing P is related to the proportion of the methyl functional which remains connected to the Si backbone. Chain crosslinking and film density are affected by this structural modification induced by homogeneous and heterogeneous plasma reactions. The density increase resulted in a film with hardness comparable to that of the silica and more resistant to the permeation of oxidative species, but preserving the organosilicon nature of the structure. Full article