Electrical properties of silicon nitride films deposited by catalytic chemical vapor deposition on catalytically nitrided Si(100)

Thin film transistor incorporating silicon nitride (SiN_x) films deposited by catalytic chemical vapor deposition (Cat-CVD) on silicon exhibit some problems such as a large-threshold voltage shift and a large hysteresis loop width of the capacitance vs. voltage (C–V) characteristics. In this work, in order to solve these problems, the surface of the silicon substrate is catalytically nitrided before SiN_x deposition. Inserting the nitridation layer, injection-type hysteresis loop of C–V curve is reduced from 1.3 to 0.05 V and large threshold voltage shift to the negative direction is reduced from 4 to 1.8 V.     

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.     

A mechanistic study of gas-phase reactions with 1,1,3,3-tetramethyl-1,3-disilacyclobutane in the hot-wire chemical vapor deposition process

The gas-phase chemical species produced from both the direct decomposition of 1,1,3,3-tetramethyl-1,3-disilacyclobutane (TMDSCB) on a tungsten filament and the secondary reactions in the HWCVD reactor were identified by vacuum ultraviolet laser single-photon ionization coupled with time-of-flight mass spectrometry. TMDSCB decomposes on the filament to methyl and 1,1,3-trimethyl-1,3-disilacyclobutane-1-yl radicals. Subsequent hydrogen abstraction reactions from the parent molecule by methyl radicals and biradical combination reactions are dominant in the reactor. The formation of dimethylsilene (m/z = 72) through the ring Si-C bond cleavage is indirectly confirmed by the observation of the signal from 1,1,3,3,5,5-hexamethyl-1,3,5-trisilacyclohexane at m/z = 216. Tetra- and tri-methylsilane are also found to be formed in the HWCVD reactor.     

Preparation of ZrC-SiC composite coatings by chemical vapor deposition and study of co-deposition mechanism

In this work, the ZrC-SiC composite coatings were co-deposited by chemical vapor deposition (CVD) using ZrCl₄, MTS, CH₄ and H₂ as raw materials. The morphologies, compositions and phases of the composite coatings were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The results indicated that the morphologies, compositions and phases of the composite coatings were related to the deposition temperature, the flow rate of the carrier H₂ gas, and the ratio of C/Zr. Moreover, the co-deposition mechanism of the composite coatings was also studied. It was found that different deposition temperatures resulted in different deposition mechanisms. At temperatures in the range of 1150–1250 °C, the ZrC-SiC co-deposition was controlled by the surface kinetic process. At temperatures in the range of 1250–1400 °C, the ZrC-SiC co-deposition was controlled by the mass transport process.     

Deposits obtained by photolysis of hexamethyldisilane by ArF excimer laser (SiC thin film preparation by ArF excimer laser chemical vapor deposition, Part 2)

Thin films have been prepared by decomposition of hexamethyldisilane (HMDS) by ArF excimer laser at the fixed laser fluence of 800 J m⁻² and the substrate temperatures from 300 to 673 K and have been characterized using X-ray diffraction (XRD), scanning electron microscope observation, IR reflection spectroscopy and X-ray photoelectron spectroscopy. The XRD patterns showed the formation of 3C-SiC films but it is suggested that the films obtained at lower substrate temperature include organic functional groups, which might be derived from gaseous reaction products. Hydrogen existing in the form of Si-CH₂-Si could be decreased by decreasing the partial pressures of HMDS.     

Silicon nanorods prepared by glancing angle catalytic chemical vapor deposition

Vertically oriented amorphous and microcrystalline Si nanorods grown on different substrates were successfully obtained by Cat CVD with the glancing angle incident silane flux at low temperatures. The influences of the substrate type, substrate temperature, post treatment and hydrogen dilution on the microstructure of Si nanorods were investigated. The density and diameter of nanorods are varying with the substrates. The hydrogen dilution of silane dominates the crystallization of Si nanorods rather than high substrate temperature at 550 °C and annealing at 900 °C in nitrogen for 6 h. The crystallized Si nanorods with crystalline volume fraction, Xc, of 0.55 were achieved under a low substrate temperature of 140 °C.     

Effect of growth parameters on the heteroepitaxy of 3C-SiC on 6H-SiC substrate by chemical vapor deposition

Epitaxial 3C-SiC(1 1 1) films were grown on 6H-SiC(0 0 0 1) Si face on axis substrates by chemical vapor deposition under H₂, SiH₄ and C₃H₈ in a cold wall vertical reactor. Two temperatures were studied (1450 and 1700 °C) with various C/Si ratio and deposition time. It was found that under conditions giving high lateral growth (low C/Si and/or high temperature), homoepitaxial growth occurred even at temperatures as low as 1450 °C. For other conditions, the 3C-SiC polytype was detected and always together with the formation of double positioning boundaries whose density was found to depend on the growth conditions but not on the initial surface reconstruction. Single domain enlargement was observed when growth was performed at 1700 °C over a nucleation layer grown at 1450 °C.     

Carbonized tantalum catalysts for catalytic chemical vapor deposition of silicon films

Catalytic chemical vapor deposition (Cat-CVD) has been demonstrated as a promising way to prepare device-quality silicon films. However, catalyst ageing due to Si contamination is an urgency to be solved for the practical application of the technique. In this study, the effect of carbonization of tantalum catalyst on its structure and performance was investigated. The carbonized Ta catalyst has a TaC surface layer which is preserved over the temperature range between 1450 and 1750 °C and no Si contamination occurs on the catalyst after long-term use. Si film prepared using the carbonized Ta catalyst has a similar crystal structure to that prepared by uncarbonized Ta catalyst. Formation of the TaC surface layer can alleviate the ageing problem of the catalyst, which shows great potential as a stable catalyst for Cat-CVD of Si films.     

The structure and optical properties of silicon nanowires prepared by inductively coupled plasma chemical vapor deposition

Silicon nanowires were prepared by vapor-liquid-solid (VLS) mechanism at a growth temperature as low as 380 °C in an inductively coupled plasma chemical vapor deposition system. The nanowires consist of crystalline core surrounded by a thick amorphous silicon shell. An increase in plasma power produces dense and long nanowires with thick amorphous shell, accompanied with a thick uncatalyzed amorphous silicon film on the silicon substrate. Small catalyst nanoparticles are easier activated by plasma to grow the dense and thin nanowires in comparison with the large-size nanoparticles. Moreover, an enhanced optical absorption is achieved due to the strong light trapping and anti-reflection effects in the thin and tapered silicon nanowires with high density.     

Low temperature silicon epitaxy from trichlorosilane via mesoplasma chemical vapor deposition

Epitaxial silicon thick films have been deposited at around 400 °C by mesoplasma chemical vapor deposition with trichlorosilane (TCS) as source gas. The deposition rate of the Si films increases linearly with the TCS flow rate and reaches 30 nm/s at 15 sccm of TCS. These films have exhibited relatively high hall mobility (~ 200 cm²/V-s) independently of the deposition rate.     

温度对化学气相沉积碳化硅涂层的影响

以三氯甲基硅烷和氢气为气源,研究了化学气相沉积碳化硅过程中,温度(850-1350℃)对沉积速率、反应物消耗效应、涂层形貌和相结构的影响.用磁悬浮天平在线实时称量基体质量变化进行动力学研究;采用扫描电镜和X射线衍射对样品做了表征.结果表明,沉积过程存在四个控制机理:a区(<1000℃)为表面反应动力学控制;b区(1000-1050℃)主要是HCl对沉积的抑制作用;c区(1050-1300℃)是表面化学反应和传质共同控制;d(>1300℃)为传质为限速步骤.由于不同的控制机制,导致所得涂层的形貌存在差异.含碳含硅中间物质浓度的减小、HCl增多和MTS的分解共同导致反应物消耗效应.涂层由热解碳和碳化硅两相组成,温度的升高使热解碳相减少,碳硅比接近1.     

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.     

Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method

We report the dependence of growth yield of single-walled carbon nanotubes (SWNTs) on heat-treatment time and catalyst film thickness by the alcohol catalytic chemical vapor deposition method. Three types of heat-treatment, synthesis of 30 min, synthesis of 30 min after annealing of 30 min, and synthesis of 60 min, were investigated. Thickness of Co catalyst film was varied from 1 to 10 nm. In the case of thinner Co film less than 3 nm, long synthesis time of 60 min is favorable for the effective SWNT growth, because of the small amount of Co catalyst. In the case of thicker Co film more than 3 nm, an amount of grown SWNTs by 30 min synthesis after 30 min annealing and by 60 min synthesis was much higher than that by 30 min synthesis without annealing, showing that total heat-treatment time of 60 min is important for the SWNT growth. Results suggest that the conversion from the thicker film of Co to nano-particle which acts as catalyst takes place during the first 30 min.     

Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method

We report the dependence of growth yield of single-walled carbon nanotubes (SWNTs) on heat-treatment time and catalyst film thickness by the alcohol catalytic chemical vapor deposition method. Three types of heat-treatment, synthesis of 30 min, synthesis of 30 min after annealing of 30 min, and synthesis of 60 min, were investigated. Thickness of Co catalyst film was varied from 1 to 10 nm. In the case of thinner Co film less than 3 nm, long synthesis time of 60 min is favorable for the effective SWNT growth, because of the small amount of Co catalyst. In the case of thicker Co film more than 3 nm, an amount of grown SWNTs by 30 min synthesis after 30 min annealing and by 60 min synthesis was much higher than that by 30 min synthesis without annealing, showing that total heat-treatment time of 60 min is important for the SWNT growth. Results suggest that the conversion from the thicker film of Co to nano-particle which acts as catalyst takes place during the first 30 min.     

Synthesis of silicon carbide nanowires by solid phase source chemical vapor deposition

In this paper, we report a simple approach to synthesize silicon carbide (SiC) nanowires by solid phase source chemical vapor deposition (CVD) at relatively low temperatures. 3C-SiC nanowires covered by an amorphous shell were obtained on a thin film which was first deposited on silicon substrates, and the nanowires are 20–80 nm in diameter and several μm in length, with a growth direction of [200]. The growth of the nanowires agrees well on vapor-liquid-solid (VLS) process and the film deposited on the substrates plays an important role in the formation of nanowires.     

Hydrogen storage of a mechanically milled carbon material fabricated by plasma chemical vapor deposition

Abstract

Carbon materials were prepared by plasma chemical vapor deposition at different pressures without catalyst, and the structure and hydrogen storage characteristics of milled and unmilled samples of the materials were evaluated. Using this approach, we were able to fabricate graphite microcrystals with a crystallite size of several nanometers, and the crystallite size and surface area could be controlled by changing the pressure during plasma chemical vapor deposition. The hydrogen storage capacity of the unmilled materials was 0.3?wt%, but milling increased this value to 1.0?wt% by reducing the crystallite size and increasing the crystallite surface area.     

Chemical vapor deposition of phase-rich WC thin films on silicon and carbon substrates

Chemical vapor deposition was used to deposit tungsten carbide from a mixture of WCl₆, H₂ and C₃H₈ at 750-1050 °C on silicon and carbon substrates. The phase composition of the films was correlated with substrate temperature, substrate position in the reactor, and total flow rates. X-ray diffraction and X-ray photoelectron spectroscopy were employed to investigate the surface and bulk properties of the thin films. Thick, adherent films of phase-rich hexagonal WC were deposited using 1.3 × 10³ Pa total pressure, 1050 °C substrate temperature, and reactant flow rates of H₂/C₃H₈/Ar/WCl₆ = 1.8 × 10^− 2/3.6 × 10^− 3/8.9 × 10^− 4/1.8 × 10^− 4 mol/min, where Ar is the carrier gas. The surface composition was oxygen and carbon rich as compared with the bulk.     

Silicidation and carburization of the tungsten filament in HWCVD with silacyclobutane precursor gases

Study of the tungsten filament alloying processes with different precursor molecules shows that silicidation occurs when using silacycobutane (SCB) and carburization with 1,1,3,3-tetramethyl-1,3-disilacyclobutane (TMDSCB). The difference in the decomposition chemistry with the two molecules is responsible for the observation. Comparison of the depth profile and temperature distribution of the Si or C content in the alloyed filament illustrates the interplay among the Si or C deposition onto, evaporation from, and diffusion into the filament. Examination of the time distribution of key products from secondary gas-phase reactions at various filament temperatures demonstrates that gas-phase reactions dominate only at low temperatures. Silicidation or carburization is the dominant process at high temperatures, which contributes to a large consumption rate of precursor gas and a reduction in formation rate of the gas-phase reaction products.     

Fabrication of PTFE thin films by dual catalytic chemical vapor deposition method

Dependence of catalyzing materials on deposition of polytetrafluoroethylene (PTFE = ”Teflon” in commercial) films by catalytic chemical vapor deposition (Cat-CVD) method is investigated. It has been clarified that Ni-containing catalyzers has a catalyzing effect that can decompose hexafluoropropylene-oxide (HFPO) to form PTFE films. A novel method named Dual Cat-CVD is also proposed. In the method, carbonized and fluorinated surface of Ni-containing catalyzer is removed and refreshed using atomic hydrogen generated by additionally introduced tungsten (W) catalyzer in the same chamber. This Dual Cat-CVD method enables to recover the deposition rate of PTFE films drastically.     

Rheotaxial diamond growth by chemical vapor deposition

This paper is to report a novel method to synthesize diamond crystal by using a well developed chemical vapor deposition process, but on a liquid substrate, while substrates of prevailing practice are solid. The substrate materials are metals which become liquid at diamond deposition temperature, such as elements Sn and Ga, and eutectic alloys of Cu-Ge, Sn-Ge. One result is that, while reported diamond crystal size was about 10 to 40 micrometers on the solid substrate, on the liquid substrate, the crystal size has reached so far about 300 micrometers. Received: 17 May 2000 / Reviewed and accepted: 8 June 2000