Study on W/SiC interface of SiC fiber fabricated by chemical vapor deposition on tungsten filament

SiC fiber was fabricated by chemical vapor deposition on tungsten filament heated by direct current in a CH₃SiCl₃-H₂ gas system. Microstructure of W/SiC interfacial reaction zone in the fiber was identified by means of scanning electron microscope and transmission electron microscope. Results showed that the thickness of the interfacial reaction zone is between 350 and 390 nm, and two reaction products of W₅Si₃ and WC were formed during fabricating SiC fiber. Electron diffraction analysis and composition detection indicated that W₅Si₃ is adjacent to tungsten core and WC is adjacent to SiC sheath, and the W/SiC interface can be described as W/W₅Si₃/WC/SiC. Furthermore, the formation mechanism of the interfacial reaction zone is discussed.     

Fabrication of low-resistivity and gold-colored TiN films by halide chemical vapor deposition with a low [NH3]/[TiCl4] flow ratio

This work describes the preparation of titanium nitride (TiN) films on Si (111) substrates by atmospheric pressure halide chemical vapor deposition (AP-HCVD). Various TiN films were obtained by exploiting TiCl₄ + NH₃ gas chemistry with flow ratios [NH₃]/[TiCl₄] from 0.2 to 1.4, and deposition temperatures (T_d) from 600 to 900 °C. When T_d = 800 °C gold-colored films with electrical resistivities of under 100 μΩ cm were formed at almost all of the investigated [NH₃]/[TiCl₄] flow ratios. In particular, a lowest resistivity of about 23.7 μΩ cm, which is quite close to that of bulk TiN, was achieved using an [NH₃]/[TiCl₄] flow ratio of 0.3. Atomic force microscopy indicated that the root mean square surface roughness of that film was only about 5.1 nm. Under the same [NH₃]/[TiCl₄] flow ratio as above, X-ray diffraction analyses revealed the presence of a cubic TiN phase with a preferred orientation of (200) for T_d ≤ 800 °C, while additional (111) and (220) orientations emerged when the film was deposited at 900 °C. In conclusion, a low resistivity (< 100 μΩ cm) TiN film can be formed by AP-HCVD with very low [NH₃]/[TiCl₄] flow ratios 0.3-1.4.     

Orientation dependent growth of SiC nanocrystals at the SiO2/Si interface

Cubic SiC nanocrystals are formed epitaxially and void-free on single crystal Si substrate by reactive annealing in CO. In this study characterization of the nucleation, growth and morphology is presented on differently oriented single crystal Si substrates. It is found that SiC nanocrystals of various shape can be grown in different densities on the (100), (110) and (111) Si surfaces with an average size of 30-60 nm. Effect of annealing time, CO concentration, substrate orientation and crystal size on crystallite growth is discussed. Parameters to obtain increased SiC nucleation density are determined.     

Embedding of reduced pressure-chemical vapor deposition grown Ge nanocrystals in a high quality SiO2 matrix for non-volatile memory applications

We have obtained thanks to reduced pressure-chemical vapor deposition germanium nanocrystals in a high quality SiO₂ matrix. A perfect control of (i) the tunnel and control oxide layer thicknesses and (ii) the germanium nanocrystals' density and diameter has been achieved. Scanning electron microscopy was used to (i) determine the nucleation and growth rate of the germanium nanocrystals and (ii) evaluate their morphological stability during their embedding. We have also studied the influence of thin selectively grown Si films in order to passivate the surface of the germanium nanocrystals. X-ray photoelectron spectroscopy has shown that the germanium nanocrystals' surface properties are better with a Si capping. The polycrystalline state of the nanocrystals has been evaluated with X-ray diffraction. Transmission electron microscopy image reveals the lack of germanium diffusion and precipitation in the SiO₂ matrix.     

Silicon nanostructures fabricated by Au and SiH4 co-deposition technique using hot-wire chemical vapor deposition

In this study, the fabrication of Si nanostructures by Au and SiH₄ co-deposition technique using hot-wire chemical vapor deposition was demonstrated. A high deposition rate of 2.7 nm/s and a high density of silicon nanostructures with a diameter of about 140 nm were obtained at T_s of 250 °C. An increase in T_s led to a significant reduction in the size of the nanostructures. However, coalescence on the nanostructures was observed at T_s of 400 °C. The Si nanostructures exhibited a highly crystalline structure, which was induced by Au crystallites. The crystallite size and crystallinity of the Si nanostructures amplified with the increase in T_s. The presence of nanostructures enhanced the surface roughness of the samples and clearly reduced the reflection, especially in the visible region.     

Characterization of SiNx:H films deposited by rapid thermal chemical vapor deposition

Hydrogenated silicon nitride films were deposited with NH₃, SiH₄ and N₂ gas mixture at 700 °C by rapid thermal chemical vapor deposition (RTCVD) system. The NH₃/N₂ flow ratio and deposition pressure are found to influence the film properties. The stress of SiN_x:H films deposited by RTCVD is tensile, which can reach ~ 1.5 GPa in our study. The stress of SiN_x:H films is dependent on the deposition parameters, which can be associated with chemical configuration of the film. It is suggested that the presence of hydrogen atoms will relax the Si-N network, which results in the decrease of tensile stress of the SiN_x:H film.     

Formation of size-controlled silicon nanocrystals in plasma enhanced chemical vapor deposition grown SiOxNy/SiO2 superlattices

Size controlled silicon nanocrystals (SiNC) in silicon oxynitride matrix were prepared using plasma enhanced chemical vapor deposition. The as-deposited superlattices (SLs) and the corresponding bulk films were treated by thermal annealing. Hydrogen effusion was performed during the heating up by choosing a sufficiently low heating ramp. The phase separation of the layers into SiNCs and surrounding oxynitride matrix was studied at temperatures of up to 1150 °C. The influence of the annealing temperature on SiO_xN_y/SiO₂ - SLs with varying SiO_xN_y layer thickness was investigated by several analytical techniques including variable angle spectroscopic ellipsometry, photoluminescence (PL) spectroscopy, x-ray photoelectron spectroscopy, Fourier transform infrared spectrometry (FTIR) and transmission electron microscopy (TEM). Before annealing FTIR investigations show in addition to the expected Si-O bonds also the formation of nitrogen and hydrogen related bonds. The shift of the Si-O-Si stretching vibration to higher wave numbers after annealing indicates phase separation. The disappearance of the hydrogen related bonds indicates the hydrogen effusion. The PL signal is rising significantly with increasing annealing temperature and the PL peak position is strongly related to the thickness of the SiO_xN_y sublayers due to quantum confinement effects. TEM investigations confirm the size-controlled growth of SiNCs within the oxynitride matrix. The role of incorporated nitrogen and hydrogen is discussed.     

Single-source chemical vapor deposition of clean oriented Al2O3 thin films

Clean oriented Al₂O₃ thin film with a dominant Al₂O₃ <1 1 3> plane was deposited on Si <1 0 0> substrate at 550 °C, by single-source chemical vapor deposition (CVD) using aluminium(III) diisopropylcarbamate, Al₂(O₂CNⁱPr₂)₆. This process represents a substantial reduction in typical CVD film growth temperatures which are typically > 1000 °C. Through the studies of thermal stability of this precursor, we propose a specific β-elimination decomposition pathway to account for the low temperature of the precursor decomposition at the substrate, and for the lack of carbon impurity byproducts in the resulting alumina films that are characterized using X-ray photoelectron spectroscopy and depth profiling.     

Improvement of the properties and electrical performance on TiCl4-based TiN film using sequential flow chemical vapor deposition process

Sequential flow chemical vapor deposition (SFCVD), utilizing TiCl₄/NH₃ as reactants and immediate NH₃ treatment after film deposition, is applied to produce TiN barrier films in the contact process. Secondary ion mass spectroscopy results indicate that the SFCVD TiN film can effectively block the diffusion of WF₆ into the underlying Ti layer during W deposition. NH₃ treatment immediately after film deposition causes SFCVD TiN films to be less contaminated with carbon than TiN films that are formed by metallic organic compounds chemical vapor deposition (MOCVD) and to contain less chlorine residue than conventional TiCl₄/NH₃ CVD TiN layers even at a low reaction temperature. According to the resistance measurement of Kelvin contacts, the SFCVD process yields a lower resistance and a more uniform distribution than the MOCVD or CVD process. Transmission electron microscopic observations demonstrate that WF₆ can diffuse through the MOCVD TiN to react with the underlying Ti layer, causing a rupture at the Ti/TiN interface and poor W adhesion. The SFCVD TiN can serve as a sufficient diffusion barrier against WF₆ penetration during W CVD deposition.     

Highly (100)-oriented CeO2 films prepared on amorphous substrates by laser chemical vapor deposition

CeO₂ films were prepared on amorphous silica substrates by laser chemical vapor deposition using cerium dipivaloylmethanate precursor and a semiconductor InGaAlAs (808 nm in wavelength) laser system. The laser spot size was about 20 mm, which was sufficient to cover the whole substrate. Highly (100)-oriented CeO₂ films were obtained at extraordinary high deposition rates ranging from 60 to 132 μm/h. Films exhibited a columnar feather-like structure with a large number of nano-sized voids, and a surface morphology consisting of either nearly flat or pyramidal top-ending columns depending on the laser power. Nearly flat top-ending columns could be fairly (100)-oriented at the top and (111)-oriented laterally.     

微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石

研究了衬底温度、核化密度、衬底表而预处理等工艺参数对微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石的影响.采用扫描电镜、X-射线衍射、喇曼光谱和红外光谱对样品进行了表征.结果表明:从高核化密度生长的金刚石膜中探测不到碳化硅;不论对硅衬底进行抛光预处理还是未抛光预处理,从低核化密度牛长的金刚石厚膜中总能探测到碳化硅.碳化硅生长在硅衬底上未被金刚石覆盖的地方,或者是在金刚石晶核之间的空洞处.碳化硅形成和金刚石生长是同时发生的两个竞争过程.此研究结果为制备金刚石和碳化砟复合材料提供了一种新的方法.     

BiFeO3 thin films prepared using metalorganic chemical vapor deposition

BiFeO₃ thin films were grown on (001) SrTiO₃ and (001) ZrO₂(Y₂O₃) substrates by single source metalorganic chemical vapor deposition in the temperature range T = 500 ÷ 800 °C using Fe(thd)₃ and Bi(C₆H₅)₃ as volatile precursors. X-ray diffraction analysis shows cube-on-cube epitaxial growth of BiFeO₃ on (001) SrTiO₃. The strongly reduced bismuth transfer into the film due to the high thermal stability of Bi(C₆H₅)₃ was counterbalanced by the increase of the total pressure as well as of the residence time of the precursor flow in the reactor; the Bi/Fe ratio in the film thus becomes close to that in the precursor mixture. Optical second harmonic generation measurements have evidenced the ferroelectric ordering in BiFeO₃ films and the apparent decrease of the Curie temperature of the strained films as compared to BiFeO₃ single crystal.     

Synthesis of binary and triple carbon nanotubes over Ni/Cu/Al2O3 catalyst by chemical vapor deposition

Novel binary and triple carbon nanotubes (CNTs) with one common catalytic particle encapsulated have been synthesized using Ni/Cu/Al₂O₃ catalyst, which was produced by a sol-gel method. But when using Ni/Al₂O₃ as catalyst, a mass of common CNTs, that is, one CNT with one catalytic particle encapsulated, was obtained. The results showed that copper-element doping to the Ni/Al₂O₃ catalyst played a key role in the synthesis of CNTs, signifying a novel approach to modify the Ni/Al₂O₃ catalyst. Based on the transmission electron microscopy observations, a simple growth mechanism was developed to describe the growth of the binary or triple CNTs, which could be well explained by a diffusion segregation process.     

Preparation of Magnéli phases of Ti27O52 and Ti6O11 films by laser chemical vapor deposition

Magnéli phases of Ti₂₇O₅₂ and Ti₆O₁₁ films were prepared by laser chemical vapor deposition using Ti(dpm)₂(O-i-Pr)₂ as a precursor. Ti₆O₁₁ film was obtained at a laser power (P_L) of 200 W and a deposition temperature (T_dep) of 1270 K. Ti₂₇O₅₂ film was obtained at P_L = 150 to 200 W and T_dep = 1120 to 1250 K. Ti₆O₁₁ and Ti₂₇O₅₂ films had a faceted texture about 2 μm in grain size and a columnar cross section. The deposition rate of Ti₂₇O₅₂ and Ti₆O₁₁ films were 90 and 70 μm h^− 1, respectively.     

Growth of silicon carbide thin films by hot-wire chemical vapor deposition from SiH4/CH4/H2

Silicon carbide (SiC) thin films were prepared by hot-wire chemical vapor deposition from SiH₄/CH₄/H₂ and their structural properties were investigated by X-ray diffraction, Fourier transform infrared absorption and Raman scattering spectroscopies. At 2 Torr, Si-crystallite-embedded amorphous SiC (a-Si_1 − xC_x:H) grew at filament temperatures (T_f) below 1600 °C and nanocrystalline cubic SiC (nc-3C-SiC:H) grew above T_f = 1700 °C. On the other hand, At 4 Torr, a-Si_1 − xC_x:H grew at T_f = 1400 °C and nc-3C-SiC grew above T_f = 1600 °C. When the intakes of Si and C atoms into the film per unit time are almost the same and H radicals with a high density are generated, which takes place at high T_f, nc-3C-SiC grows. On the other hand, at low T_f the intake of Si atoms is larger than that of C atoms and, consequently, Si-rich a-Si_1 − xC_x:H or Si-crystallite-embedded a-Si_1 − xC_x:H grow.     

Properties of nanocrystalline SiC:Ge:H alloy deposited by hot-wire chemical vapor deposition using Organosilane and Organogermane

Nanocrystalline hydrogenated silicon carbide: germanium alloy (nc-SiC:Ge:H) films have been deposited by hot-wire chemical vapor deposition at a low substrate temperature of about 300 °C. Germanium incorporation into the films and film structure based on cubic silicon carbide were confirmed by X-ray photoelectron spectroscopy and X-ray diffraction. Optical absorption spectra of the films with a germanium mole fraction of about 2% shifted to lower energies by about 0.2 eV compared with that of nanocrystalline cubic silicon carbide films.     

Deposition of nanocrystalline translucent h-BN films by chemical vapor deposition at high temperature

h-BN layers were deposited on α-SiC and sapphire substrates by chemical vapor deposition at high temperature (1500-1900 °C) using B₂H₆ and NH₃ diluted in Ar. Growth rates were in the 6-10 μm/h range. In all the conditions studied, the as deposited BN layers were found to be translucent to light, some having a light whitish aspect and other a more yellowish one. It was also observed that the deposit was not always adhesive. Characterizations showed that the layers were nano-crystalline with crystallite size < 10 nm. The growth rate was found to be temperature and N/B ratio dependent due to an N limited growth regime which is more pronounced above 1700 °C.     

Carbon dioxide as a carbon source for synthesis of carbon nanotubes by chemical vapor deposition

Carbon dioxide was successfully used as carbon source in the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) over Fe/CaO catalyst. The product was evaluated using both transmission electron microscopy (TEM) and Raman spectroscopy. Crooked and branching structures of multi-walled carbon nanotubes (MCNTs) with diameters of around 50 nm were observed on the TEM micrographs. Raman spectrum results show that the nanotubes have small defects, which is in agreement with the results of TEM. The influence of reaction variable such as furnace temperature and types of support media was also studied and the reaction mechanism was then discussed in this paper.     

Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2) tungsten complex (CH3CN)Cl4W(NNMe2)

Tungsten nitride carbide (WN_xC_y) thin films were deposited by chemical vapor deposition using the dimethylhydrazido (2⁻) tungsten complex (CH₃CN)Cl₄W(NNMe₂) (1) in benzonitrile with H₂ as a co-reactant in the temperature range 300 to 700 °C. Films were characterized using X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy and four-point probe to determine film crystallinity, composition, atomic bonding, and electrical resistivity, respectively. The lowest temperature at which growth was observed from 1 was 300 °C. For deposition between 300 and 650 °C, AES measurements indicated the presence of W, C, N, and O in the deposited film. The films deposited below 550 °C were amorphous, while those deposited at and above 550 °C were nano-crystalline (average grain size < 70 Å). The films exhibited their lowest resistivity of 840 µΩ-cm for deposition at 300 °C. WN_xC_y films were tested for diffusion barrier quality by sputter coating the film with Cu, annealing the Cu/WN_xC_y/Si stack in vacuum, and performing AES depth profile and XRD measurement to detect evidence of copper diffusion. Films deposited at 350 and 400 °C (50 and 60 nm thickness, respectively) were able to prevent bulk Cu transport after vacuum annealing at 500 °C for 30 min.     

Low temperature chemical vapor deposition of nanocrystalline V2O5 thin films

Spatially uniform, carbon-free thin films of V₂O₅ were deposited on silicon by chemical vapor deposition using vanadium oxide triisopropoxide and water as gaseous precursors, in the temperature range of 100-300 °C. Films with substantial crystallinity were obtained for deposition temperatures as low as 180 °C. The “neat” chemistry that nominally leaves no fragments of ligand or water in the solid promotes film purity and reduces the deposition temperature needed for crystallization. Such deposition temperatures also open up additional possibilities for using crystalline vanadia on fragile substrates such as polymers for electronics and optical applications.