Surface nano-structured silicon carbide thin film produced using hot filament decomposition of ethylene at low temperature on silicon wafer

The structure and spectroscopic properties of nano-structured silicon carbide (SiC) thin films were studied for films obtained through deposition of decomposed ethylene (C₂H₄) on silicon wafers via hot filament chemical vapor deposition method at low temperature followed by annealing at various temperatures in the range 300-700 °C. The prepared films were analyzed with focus on the early deposition stage and the initial growth layers. The analysis of the film's physics and structural characteristics was performed with Fourier transform infrared spectroscopy and Raman spectroscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, and X-ray diffraction. The conditions for forming thin layer of cubic SiC phase (3C-SiC) are found. X-ray diffraction and Raman spectroscopy confirmed the presence of 3C-SiC phase in the sample. The formation conditions and structure of intermediate SiC layer, which reduces the crystal lattice mismatch between Si and diamond, are essential for the alignment of diamond growth. This finding provides an easy way of forming SiC intermediate layer using the Si from the substrate.     

Growth and characterisation of SiC films deposited on a-SiO2/Si (100) substrates

Abstract

The growth of polycrystalline SiC films has been carried out by low pressure chemical vapour deposition in a horizontal quartz reaction chamber using tetramethylsilane and H2 as the precursor gas mixture. Silicon (100) wafers were used as substrates. A thin Si O₂ amorphous layer of ~6 nm was formed before SiC deposition to reduce the strain induced by the 8% difference in thermal expansion coefficients between SiC and Si. Samples were. analysed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and infrared reflectivity. The structure of films grown at temperatures between 950 and 1150°C varies from amorphous to polycrystalline SiC. Preferential [111] orientation and columnar growth of polycrystalline films develops with increasing temperature.

MST/3317     

Pressure dependent structural and optical properties of silicon carbide thin films deposited by hot wire chemical vapor deposition from pure silane and methane gases

Silicon carbide (SiC) thin films were deposited using hot wire chemical vapor deposition technique from silane (SiH₄) and methane (CH₄) gas precursors. The effect of deposition pressure on structural and optical properties of SiC films was investigated. Various spectroscopic methods including Fourier transform infrared spectroscopy, Raman scattering spectroscopy, Auger electron spectroscopy, and UV–Vis–NIR spectroscopy were used to study these properties. Films deposited at low deposition pressure were Si-rich, and were embedded with nano-crystals of silicon. These films showed strong absorption in the visible region and had low energy band gaps. Near stoichiometric SiC film, were formed at intermediate deposition pressure and these films were transparent in the visible region and exhibited a wide optical band gap. High deposition pressures caused inhomogeneity in the film as reflected by the increase in disorder parameter and low refractive index of the films. This was shown to be due to formation of sp ² carbon clusters in the film structure.     

Si-rich a-SiC:H thin films: Structural and optical transformations during thermal annealing

Amorphous hydrogenated silicon-rich silicon carbide (a-Si_0.8C_0.2:H) thin films were prepared by plasma enhanced chemical vapour deposition and were thermally annealed in a conventional resistance heated furnace at annealing temperatures up to 1100 °C. The annealing temperatures were varied and the samples were characterised with Auger electron spectroscopy, glancing incidence X-ray diffraction, Raman spectroscopy, Fourier transformed infrared spectroscopy, transmission electron microscopy and photoluminescence (PL) spectroscopy. As-deposited a-Si_0.8C_0.2:H thin films contain a large amount of hydrogen and are amorphous. When annealing the films, the onset of Si crystallisation appears at 700 °C. For higher annealing temperatures, we observed SiC crystallites in addition to the Si nanocrystals (NCs). The crystallisation of SiC correlates with the occurrence of a strong PL band, which is strongly reduced after hydrogen passivation. Thus PL signal originates from the SiC matrix. Si NCs exhibit no PL yield due to their inhomogeneous size distribution.     

Physicochemical and structural characteristics of TiC and VC thin films deposited by DC reactive magnetron sputtering

Vanadium carbide and titanium carbide films were deposited on Si substrates by direct current reactive magnetron sputtering, varying the substrate temperature during deposition and the reactive gas (CH₄) pressure. The physicochemical and structural properties of the films were characterized for stoichiometric films (V/C = 1 and Ti/C = 1), which display good performance concerning wear, friction, and corrosion. The techniques used to characterize the films were Rutherford backscattering spectrometry in channeling geometry, ¹²C(α,α)¹²C nuclear resonant scattering, glancing angle X-ray diffraction, X-ray reflectometry, and X-ray photoelectron spectroscopy. The results revealed that the ideal conditions for deposition of these films are a CH₄ partial pressure of 0.5 × 10⁻³ mbar and a substrate temperature of 400 °C. In such conditions, the deposition rates are 7 nm s⁻¹ for TiC and 8.5 nm s⁻¹ for VC at a target power density of 5.5 W cm⁻². The density of the films, as determined here by X-ray reflectometry, are slightly higher than those for the bulk materials.     

Gas tunnel type plasma spraying deposition and microstructure characterization of silicon carbide films for thermoelectric applications

Gas tunnel type plasma spraying deposition has been applied successfully to the deposition of the SiC films on stainless-steel substrates. The microstructure and the surface morphology of the SiC films were characterized by means of X-ray diffraction (XRD) and scanning electron microscope (SEM). The control of the processing parameters such as powder feeding rate, composition of plasma working gases, spraying distance, and carrier gas flow rate allowed the deposition of dense, uniform, continuous, and high purity crystalline SiC films. The thickness of the SiC films varied from 3 to 10 μm. EDS analysis confirmed the presence of SiO₂ in the deposited SiC films.     

Effect of hydrogen on the structure of high-rate deposited SiC on Si by atmospheric pressure plasma chemical vapor deposition using high-power-density condition

Using the atmospheric pressure plasma chemical vapor deposition (AP-PCVD) technique, SiC films were fabricated from the gas mixture of He, H₂, SiH₄ and CH₄ on silicon substrates. High-power-density condition was adopted to sufficiently activate the reactive gas molecules in the plasma. The structure, composition and crystallinity of the films were investigated as functions of the H₂ concentration in the gas mixture and substrate temperature. It was shown that increase in H₂ concentration in the plasma atmosphere reduced the growth temperature of polycrystalline SiC film. As a result, polycrystalline 3C-SiC film of which grain size was of the order of 10 nm could be grown at a substrate temperature of 820 K with a deposition rate of approximately 6.7 nm/s. It was suggested that atomic hydrogen generated with addition of H₂ in the gas mixture considerably affects not only the reaction process at the film-growing surface but also the form of precursors in the atmospheric pressure plasma. The results indicated the possibility of realizing the columnar growth of large 3C-SiC grains on Si substrate when the H₂ concentration and the VHF power were simultaneously increased in the AP-PCVD process.     

Nano-crystalline CVD diamond films deposited on cemented carbide using high current extended DC arc plasma process

Nano-crystalline diamond (NCD) films have been grown on cemented carbide substrates by high current extended DC arc plasma process using Ar/H₂/CH₄ gas mixture at low gas pressure. The plain view and cross section of films are characterized with scanning electron microscopy. A uniform and smooth surface morphology of NCD thin films is observed. Raman spectroscopy has been used to investigate purity of the NCD films. Experimental results on the synthesis and characterization of the NCD films on cemented carbide substrates are discussed in this article.     

金刚石/碳化硅复合梯度膜制备研究

采用微波等离子化学气相沉积(MW-PCVD)制备金刚石/碳化硅复合梯度膜.工作气体为H₂,CH₄和Si[CH₃]₄(四甲基硅烷,TMS),其中H₂∶CH₄=100∶0.6,Si[CH₃]₄为0％-O.05％,沉积压力为3300Pa,基体温度为700℃,微波功率为700W.基体为单晶硅,在沉积前用纳米金刚石颗粒处理.沉积后的样品经扫描电子显微镜(SEM),电子探针显微分析(EPMA),X射线能量损失分析(EDX)表明:沉积膜中的碳化硅含量是随Si[CH₃]₄流量的变化而改变.通过改变Si[CH₃]₄的流量可以制备金刚石/碳化硅复合梯度膜,且梯度膜中金刚石与复合膜过渡自然平滑.     

Analysis of nanostructured coatings synthesized by ballistic impaction of nanoparticles

SiC nanostructured coatings were synthesized by ballistic impaction of nanoparticles using a process called hypersonic plasma particle deposition (HPPD). X-ray diffraction spectra of typical samples showed the presence of crystalline SiC and Si. Grain sizes obtained through transmission electron microscopy showed particles in the sub 10 nm range with primarily crystalline β-SiC and some crystalline Si particles present. These results correlate well with particle size distributions measured using an aerosol sampling probe coupled to a scanning electrical mobility spectrometer. Interestingly, particle size distributions indicated only small changes in the particle size distributions when Si deposition was compared to SiC. Examination of adhesion characteristics highlighted the importance of a chemically bound interlayer during SiC deposition on Mo and steel substrates.     

Formation of microcrystalline SiC films by chemical transport with a high-pressure glow plasma of pure hydrogen

The formation of microcrystalline 3C-SiC films on Si substrates by the plasma-enhanced chemical transport method was investigated using a pure hydrogen glow plasma at 0.027 MPa. In this method, no source gas was necessary. Instead, the erosion products of a sintered 3C-SiC plate in a hydrogen plasma were used as the deposition source. By Fourier transform infrared (FT-IR) absorption gas analysis, the species generated by the hydrogen etching of sintered SiC were found to be SiH₄ and CH₄, which can serve as precursors for SiC film formation. The etch rate of sintered SiC by hydrogen plasma decreased with increasing source temperature. The maximum etch rate of the sintered SiC was 450 nm/min at an input power of 47 W/cm². Films prepared by this method at substrate temperatures (T_sub) of 600 and 1073 K were analyzed by FT-IR absorption spectroscopy. An absorption peak at 800 cm^- 1 related to Si-C bonds was clearly observed, but no significant hydrogen-related absorption peaks, such as C-H and Si-H, were observed in the prepared films. The deposition rate of SiC was about 8 nm/min, independent of T_sub. The SiC films had a columnar structure, and their surface morphologies revealed faceted growth. With decreasing T_sub, the lateral grain size became large. The current-voltage characteristics of a prepared SiC/Si heterojunction np diode showed rectifying behavior, demonstrating that the doping of an SiC film can be achieved without a doping gas source. The dopant distribution near the SiC/Si interface deduced from capacitance-voltage measurements suggests that the precise control of the initial growth stage is important to obtain a good SiC/Si interface.     

SiC Particles Coated by Chromium Silicides

The interaction of chromium vapors with powderlike silicon carbide (SiC) was investigated by X-ray phase analysis, X-ray microanalysis, the EPR method, electron microscopy, and the BET method. It has been established that in the temperature range of 147 K to 2023 K under a pressure of 1.3 Pa, the main interaction product is chromium silicide (Cr₅Si₃), which forms a surface layer on SiC particles in zones with a mean temperature (T _mean) of 1773 K to 1473 K. Moreover, Cr₅Si₃ vapors passing through the disperse SiC system condense in cold-temperature zones on SiC particles and aggregates.     

Low-pressure synthesis and characterization of multiphase SiC by HWCVD using CH4/SiH4

Silicon carbide (SiC) thin films were deposited by low-pressure hot wire chemical vapor deposition (HWCVD) technique using SiH₄ and CH₄ gas precursors with no hydrogen dilution. Spectroscopic and structural properties of the films deposited at various methane flow rate (10-100 sccm) and low silane flow rate of 0.5 sccm were investigated. The use of low methane flow rate resulted in a sharp and intense Si-C peak in the Fourier transform infrared (FTIR) absorption spectra. The XRD spectra of the films showed the formation of SiC crystallites at low methane flow rate. The Raman spectroscopy measurements showed the coexistence of a-Si and SiC phases in the films. Increase in methane flow rate increased the carbon incorporation and deposition rate of the SiC films but also promoted the formation of amorphous Si and SiC phases in the films.     

Carbon occupancy of interstitial sites in vanadium carbide films deposited by direct current reactive magnetron sputtering

Vanadium carbide thin films were deposited on Si substrates by direct current reactive magnetron sputtering from a V target in Ar/CH₄ plasma, varying the Ar/CH₄ partial pressure ratio and substrate temperature. The films were characterized by glancing angle X-ray diffraction and Rutherford backscattering spectrometry. Well defined crystalline structures were obtained for CH₄ content higher than 13%. The increase of substrate temperature during deposition diminishes the film thickness slightly while diminishing substantially the C/V atomic ratio. The intensity ratio of the Bragg peaks (111)/(200) decreases for increasing substrate temperature. This result is discussed in terms of a proposed mechanism for interstitial diffusion of carbon atoms in vanadium carbide thin films with fcc-like crystalline structure and the temperature dependence of carbon occupancy of tetrahedral or octahedral interstitial sites.     

Synthesis and characterization of 4H-SiC on C-plane sapphire by C60 and Si molecular beam epitaxy

4H-SiC (silicon carbide) films were grown on (0001) sapphire substrate at rather low temperatures(1000-1100 °C) with relative high deposition rate by using fullerene (C₆₀) and silicon solid sources molecular beam epitaxy with substrate nitridation and aluminum nitride (AlN) buffer layer deposition prior to the SiC deposition. The effects of substrate nitridation and AlN buffer layer to the adhesion of the SiC thin films on sapphire have been studied. X-Ray diffraction, pole figure, atomic force microscope, Fourier transform infrared spectroscopy and photoluminescence were employed for the analysis of composition, orientation of the film and surface morphology. Relative high deposition rate at ∼ 165 nm/h was achieved.     

Ultrafast thermal plasma physical vapor deposition of thick SiC films

Thick silicon carbide films have been successfully deposited at a deposition rate of 125 nm/s on stationary graphite substrates by the thermal plasma physical vapor deposition technique, with ultrafine SiC powder fed into a hybrid plasma jet and completely evaporated. The relationship between the processing parameters and the morphology, deposition rate, composition and crystal structure has been investigated under the typical conditions of substrate temperature in the range of 1400–1700 °C and chamber pressure of 250 Torr, and compared with the results of rotating substrate deposition at the substrate temperature of around 750 °C. It was found that the deposition rate and composition showed different processing parameter dependences for rotating substrate deposition and stationary substrate deposition. The films showed dense cross-sections or cauliflower-like structures depending on the deposition conditions.

©2003 Elsevier Science Ltd. All rights reserved.     

R.F. reactive sputter deposition of hydrogenated amorphous silicon carbide films

The preparation of hydrogenated amorphous silicon carbide films by r.f. reactive sputtering of a silicon target in Ar-CH₄ gas mixtures with and without an r.f. bias on the substrates was studied. Starting with a pure silicon target and increasing monotonically the CH₄ percentage from 0% to about 10%, films with 1 ⩾ x ⩾ 0 were obtained at decreasing deposition rates. After sputtering for some hours in methane-rich gas mixtures, carbon atoms were incorporated into the silicon target surface, probably as a result of atomic peening, and nearly stoichiometric SiC films were prepared by sputtering of such a target in pure argon. The different mechanisms of film formation, deposition rate, composition, hardness, friction coefficient and stresses in the films as functions of the partial pressure of methane and the value of the r.f. bias were investigated. The IR spectra offilms with different carbon contents were analysed. The greatest hardness was found for nearly stoichiometric SiC films deposited with a bias.     

Morphological, structural and optical properties of thin SiC layer growth onto silicon by pulsed laser deposition

Crystalline silicon carbide thin layers were grown on a p-type Si(1 0 0) substrate by pulsed laser deposition (PLD) using KrF excimer laser at λ=248 nm from a 6H-SiC hot-pressed target. The target “SiC” used to elaborate our SiC films is realized from a mixture of 1SiO₂ with 3C (carbon) “1SiO₂+3C” heated in an oven at 2500 °C (the target was a hot-pressed material and supplied by Goodfellow). The morphological, structural and optical properties of SiC layers were investigated by scanning electronic microscopy (SEM), high-resolution X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS) and UV-visible spectrophotometer. XRD analysis of the target showed that this latter is a hexagonal structure (6H-SiC). The XRD pattern shows that a 1.6 μm crystalline SiC layer was formed. In addition, a SIMS analysis gives a ratio Si/C of the thin SiC layer around 1.15 but the ratio Si/C of the target was found equal to 1.06, whereas one should have 1.0. This is due to the degree of the sensitivity of the SIMS technique and due to the higher ionization efficiency of Si compared to C atoms, all these which give different ratios. It is known that the PLD technique reproduces the same macroscopic property (optical, mechanical, structural, etc.) of the target. An optical gap (E_Gap) of the SiC layer of about 2.51 eV was obtained by reflectance measurement. Finally, a crystalline thin SiC layer of 1.6 μm was elaborated using PLD method at low-temperature deposition.     

Synthesis of amorphous silicon carbonitride films by pulsed laser deposition

Silicon carbonitride (SiC_xN_y) films were grown on silicon substrates using the pulsed laser deposition (PLD) technique. A silicon carbide (SiC) target was ablated by the beam of a KrF excimer laser in a nitrogen (N₂) background gas. The morphology, structure, composition, as well as the optical and mechanical properties of the coatings were investigated as functions of the N₂ pressure (1–30 mtorr) and substrate temperature (250–650 °C). Smooth, amorphous films were obtained for all the processing parameters. The concentration of nitrogen in the deposits was found to increase when increasing the N₂ pressure, while the silicon and carbon concentrations decreased concurrently. At a N₂ gas pressure of 30 mtorr, a nitrogen content in the range of 28–34 at.% was obtained. Two growth regimes were identified as a function of the N₂ pressure. For a pressure up to 10 mtorr, highly dense and homogeneous films were observed, while textured deposits were obtained at higher pressures. The latter regime was characterized by an oxygen contamination of the coatings, whose severity increased when increasing the N₂ pressure or when reducing the deposition temperature. The hardness of the films was found to be a function of the growth regime; the highest values of the hardness were obtained in the low-pressure regime, in the range of 27–42 GPa.     

Mechanical properties and density of BC<Emphasis Type="Italic">x</Emphasis>N<Emphasis Type="Italic">y</Emphasis> films grown by low-pressure chemical vapor deposition from triethylamine borane

Boron carbonitride (BC _x N _y ) films of different compositions have been grown by low-pressure chemical vapor deposition using triethylamine borane as a single-source precursor and ammonia as an additional nitrogen source. Experiments were performed at various initial vapor compositions. The resultant films have been characterized by ellipsometry, IR spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy, nanoindentation, and surface acoustic wave spectroscopy. The mechanical properties of the films are shown to correlate with their density and chemical composition. With increasing initial ammonia partial pressure in the vapor phase, the elemental composition of the films moves away from boron carbide, approaching boron nitride, which is accompanied by a reduction in the Young’s modulus, hardness, and density of the films.