Graphene epitaxy by chemical vapor deposition on SiC

We demonstrate the growth of high quality graphene layers by chemical vapor deposition (CVD) on insulating and conductive SiC substrates. This method provides key advantages over the well-developed epitaxial graphene growth by Si sublimation that has been known for decades. (1) CVD growth is much less sensitive to SiC surface defects resulting in high electron mobilities of ～1800 cm(2)/(V s) and enables the controlled synthesis of a determined number of graphene layers with a defined doping level. The high quality of graphene is evidenced by a unique combination of angle-resolved photoemission spectroscopy, Raman spectroscopy, transport measurements, scanning tunneling microscopy and ellipsometry. Our measurements indicate that CVD grown graphene is under less compressive strain than its epitaxial counterpart and confirms the existence of an electronic energy band gap. These features are essential for future applications of graphene electronics based on wafer scale graphene growth.     

Gold-vapor-assisted chemical vapor deposition of aligned monolayer WSe2 with large domain size and fast growth rate

Orientation-controlled growth of two-dimensional (2D) transition metal dichalcogenides (TMDCs) may enable many new electronic and optical applications. However, previous studies reporting aligned growth of WSe₂ usually yielded very small domain sizes. Herein, we introduced gold vapor into the chemical vapor deposition (CVD) process as a catalyst to assist the growth of WSe₂ and successfully achieved highly aligned monolayer WSe₂ triangular flakes grown on c-plane sapphire with large domain sizes (130 µm) and fast growth rate (4.3 µm·s⁻¹). When the aligned WSe₂ domains merged together, a continuous monolayer WSe₂ was formed with good uniformity. After transferring to Si/SiO₂ substrates, field effect transistors were fabricated on the continuous monolayer WSe₂, and an average mobility of 12 cm²·V⁻¹·s⁻¹ was achieved, demonstrating the good quality of the material. This report paves the way to study the effect of catalytic metal vapor in the CVD process of TMDCs and contributes a novel approach to realize the growth of aligned TMDC flakes.

     

Effect of copper foil annealing process on large graphene domain growth by solid source-based chemical vapor deposition

Controlling the metal catalyst surface structure is a critical factor to achieve growth of large graphene domains. In this prospect, we explored the annealing process to create an oxide layer and subsequent recrystallization of Cu foil for growth of large graphene domain by the atmospheric pressure chemical vapor deposition (AP-CVD) technique. We revealed the transformation of Cu surface crystallographic structures in every step of annealing process by electron back-scattered diffraction analysis. Initially, electroless polished Cu foils are annealed in Ar and then in H₂ atmosphere to obtain a smoother surface with reduced graphene nucleation sites. The transformation of Cu grain structures at various annealing steps was confirmed, where the gas atmosphere and annealing duration have significant influence. Graphene domains with the size more than 560 µm are obtained on the processed Cu surface using polystyrene as solid precursor. It is obtained that the oxidation and recrystallization process of Cu foil surface significantly influence the nucleation density, which enable growth of larger graphene domain in the developed CVD process.     

Hot-wire chemical vapor deposition and characterization of polycrystalline silicon thin films using a two-step growth method

A two-step growth method was proposed to reduce the amorphous incubation layer in the initial growth of polycrystalline silicon (poly-Si) films prepared by hot-wire chemical vapor deposition (HWCVD). In the two-step growth process, a thin seed layer was first grown on the glass substrate under high hydrogen dilution ratios (φ ≥ 0.9), and then a thick overlayer was subsequently deposited upon the seed layer at a lower φ value. The effect of various deposition parameters on the structural properties of poly-Si films was investigated by Raman spectroscopy and transmission electron microscopy. Moreover, the electrical properties, such as dark and photo conductivities, of poly-Si films were also measured. It was found that the Si incubation layer could be suppressed greatly in the initial growth of poly-Si with the two-step growth method. In the subsequent poly-Si film thickening, a lower φ value of the reactant gases can be applied to enhance the deposition rate. Therefore, a high-quality poly-Si film can be fabricated via a two-step growth method with a sufficient growth rate using HWCVD.     

Coating of TiO2 thin films on particles by a plasma chemical vapor deposition process

TiO₂ thin films were experimentally coated on glass beads by means of a rotating cylindrical plasma chemical vapor deposition (PCVD) reactor. The morphologies and growth rates of the TiO₂ thin films before and after heat treatment were measured for various process conditions. The precursors for the TiO₂ films were generated from TTIP by plasma reactions, and they were deposited on the glass beads to become TiO₂ thin films. The TiO₂ thin films coated on the glass beads became more uniform by heat treatment. The TiO₂ thin films grew more quickly on the glass beads with increasing mass flow rate of TTIP, reactor pressure, or rotation speed of the reactor. As the applied electric power decreases, the thickness of the thin films on the glass beads increases. This experimental study shows that the use of a rotating cylindrical PCVD reactor can be a good method to coat high-quality TiO₂ thin films uniformly on particles.     

Graphene synthesis by thermal chemical vapor deposition using solid precursor

We report single layer to few layer graphene on polycrystalline nickel by chemical vapor deposition at ambient pressure using solid precursor, camphor. Investigating at a wide range of temperature, it was observed that 870 °C is better for the deposition of single layer graphene on nickel substrate. The percentage of single layer on the substrate reduced significantly with decreasing the deposition temperature. The full width half maximum of the synthesized single layer graphene was 21 cm^?1 and Raman intensity ratio of 2D to G peak was almost nine. The film was transferred to insulating substrate and measured transmittance was 85 %. Raman spectroscopy, Raman mapping, SEM and UV–visible spectrometer measurement were performed for characterization.     

Optical thin films obtained by plasma-induced chemical vapor deposition

A plasma-aided deposition technique was used to prepare thin oxide coatings by the reaction of volatile chlorides with oxygen. A 13.56 MHz r.f. supply was connected to a circular electrode on which the substrates were supported. A glow discharge was set up at pressures between 5 and 100 m Torr, and a self-bias on the electrode of between ? 100 and ? 1000 V (depending on input power and pressure) creates ion-plating conditions. GeCl₄, SiCl₄, TiCl₄ and SnCl₄ were used to prepare the corresponding dioxides. The deposition conditions (pressure, bias, gas ratios and treatment time) were varied and the resultant films examined in terms of thickness (and coating rate) and their respective indices.The films were generally smooth and highly transparent and were deposited at rates of tens of nanometres per minute. TiO₂ and SiO₂ were produced with refractive index values of 2.2 and 1.45 respectively at rates of 50 nm min^?1; these rates were found to be relatively insensitive to the gas pressure and r.f. bias.In₂O₃ films were similarly prepared from trimethyl indium vapour and O₂. These films could be electrically conducting.In contrast with earlier published work on reactive plasma deposition of oxide films, this work was carried out at ambient temperatures.     

Device-quality polycrystalline silicon films deposited at low process temperatures by hot-wire chemical vapor deposition

Device-grade undoped hydrogenated polycrystalline silicon thin films have been developed from a gas mixture of silane and hydrogen using a hot-wire chemical vapor deposition (HW-CVD) method, optimizing the deposition parameters. Proper design of the HW-CVD reactor helps to deposit a uniform quality of film over a large area (100 cm²) with a two filament configuration. Extensive studies have been made of the effects of hydrogen dilution (4–60), substrate temperature (180–400°C) and filament temperature (1500–1700°C) on the film growth. Atomic force micrographs give a quantitative estimate of roughness for these films. UV-visible ellipsometry analyses confirm their compactness and crystallinity while X-ray diffraction patterns allow for the determination of the crystallite sizes (up to 400 Å). Using a hydrogen dilution of 60, a substrate temperature of 300°C and a filament temperature of 1500°C, a dark conductivity of 2.5×10⁻⁵ S/cm and its activation energy of 0.45 eV have been obtained. For these films, the Hall mobility attains 10 cm²/V s. With these deposition parameters, the intrinsic layer of complete p–i–n HW-CVD solar cells has been realized. These cells, deposited on TCO coated Corning glass substrates, exhibit 1.8% conversion efficiency under 100 mW/cm² irradiation.     

Polycrystalline AlN films with preferential orientation by plasma enhanced chemical vapor deposition

AlN thin films for acoustic wave devices were prepared by Microwave Plasma Enhanced Chemical Vapor Deposition under different process conditions, employing Si (100) and Pt (111)/SiO₂/Si (100) substrates. The films were characterized by X-ray diffraction, Fourier transform infrared transmission spectroscopy, atomic force microscopy, scanning electron microscopy, and transmission electron microscopy. The values of the distance between the plasma and the tri-methyl-aluminum precursor injector, the radiofrequency bias potential, and the substrate temperature were central in the development of polycrystalline films. The choice of the chamber total pressure during deposition allowed for the development of two different crystallographic orientations, i.e., <0001> or <1010>. The film microstructures exhibited in general a column-like growth with rounded tops, an average grain size of about 40 nm, and a surface roughness lower than 20 nm under the best conditions.     

化学气相沉积法催化合成尺寸可控的碳微球

本研究采用化学气相沉积法,以氢氧化铝为载体负载铁为催化剂,通过催化裂解乙炔合成了碳微球,并详细探讨了催化剂以及碳微球的沉积区域对所合成的碳微球的直径的影响,通过场发射扫描电镜、能谱分析、高分辨投射电镜对产物形貌和超微观结构进行了表征和分析。结果显示,催化剂和沉积区域在某种程度上对碳微球的直径起到了一定的控制作用。     

Plasma enhanced chemical vapor deposition of silicon thin films for large area electronics

In the past 2 years major advances have been made in the understanding of silane–hydrogen plasmas. In particular, the control of the formation of clusters and even crystallites at room temperature has lead researchers to change their approach and to look for plasma conditions where clusters and crystallites contribute to the growth. In addition, hydrogen has become a key element for the growth of amorphous and microcrystalline silicon films as it can easily diffuse through the growing layers and induce their crystallization below the surface.     

Wafer scale homogeneous bilayer graphene films by chemical vapor deposition

The discovery of electric field induced band gap opening in bilayer graphene opens a new door for making semiconducting graphene without aggressive size scaling or using expensive substrates. However, bilayer graphene samples have been limited to μm(2) size scale thus far, and synthesis of wafer scale bilayer graphene poses a tremendous challenge. Here we report homogeneous bilayer graphene films over at least a 2 in. × 2 in. area, synthesized by chemical vapor deposition on copper foil and subsequently transferred to arbitrary substrates. The bilayer nature of graphene film is verified by Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. Importantly, spatially resolved Raman spectroscopy confirms a bilayer coverage of over 99%. The homogeneity of the film is further supported by electrical transport measurements on dual-gate bilayer graphene transistors, in which a band gap opening is observed in 98% of the devices.     

Microcrystalline silicon films fabricated by bias-assisted hot-wire chemical vapor deposition

Microcrystalline silicon films (μc-Si:H) were deposited on stainless steel substrates by bias-assisted hot-wire chemical vapor deposition. The effect of substrate bias and substrate temperature on the crystallinity of μc-Si:H films was studied by Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The results show that both the Raman peak position and the crystalline fraction of the μc-Si:H films deposited at 200 °C were obviously improved by introducing ?800 V substrate bias. The films deposited at 200 °C with ?800 V substrate bias show strongly sharpened Si (111) peak together with Si (220) and Si (311) peaks, which was different from a weak Si (111) peak for those deposited without substrate bias. By increasing the substrate temperature from 200 to 300 °C, while keeping the substrate bias at ?800 V, the crystallinity of the silicon films was further improved, and μc-Si:H films with crystalline fraction of 74 % was obtained.     

High-rate and wide-area deposition of epitaxial Si films by mesoplasma chemical vapor deposition

Homoepitaxial Si films have been deposited at a high rate of 200 nm s⁻¹ over a wide area of 20 mm × 80 mm by cluster-assisted mesoplasma chemical vapor deposition (MPCVD) on a moving substrate. The obtained epitaxial Si films exhibited a uniform roughness of 0.1–0.3 nm (1 × 1 μm²) and a Hall mobility of ∼240 cm² V⁻¹ s⁻¹. The results suggested that under the MPCVD the deposition precursors formed at the plasma edge could be small enough not to influence either epitaxial film structure or the film quality provided the substrate temperature is maintained above 500 °C.     

Growth and microstructures of carbon nanotube films prepared by microwave plasma enhanced chemical vapor deposition process

Well-aligned carbon nanotubes (CNTs) were grown on iron coated silicon substrates by microwave plasma enhanced chemical vapor deposition. Effect of plasma composition on the growth and microstructures of CNTs were investigated by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and optical emission spectroscopy. Morphology and microstructure of nanotubes were found to be strongly dependent on the plasma composition. Aligned bamboo-shaped nanotubes consisting of regular cone shaped compartments were observed for C₂H₂/NH₃/N₂ and C₂H₂/NH₃/H₂ gas mixtures. Randomly oriented or no nanotubes growth were observed in C₂H₂/H₂ and C₂H₂/N₂ gas mixtures respectively. CNTs grown in nitrogen rich plasma had more frequent short compartments while compartment length increased with decreasing nitrogen concentration in the plasma. Raman spectroscopy of CNTs samples revealed that CNTs prepared in nitrogen rich plasma had higher degree of disorder than those in low nitrogen or nitrogen free plasma. In-situ optical emission spectroscopy investigations showed that CN and H radicals play very important role in both the growth and microstructure of CNTs. Microstructure of CNTs has been correlated as a function of CN radical concentration in the plasma. It is suggested that presence of nitrogen in the plasma enhances the bulk diffusion of carbon through the iron catalyst particles which causes compartment formation. Based on our experimental observations, growth model of nanotubes under different plasma composition has been suggested using base growth mechanism.     

Poly-crystalline silicon thin films prepared by plasma-assisted hot-wire chemical vapor deposition

A combination of hot-wire chemical vapor deposition (HWCVD) and RF plasma, referred to as plasma-assisted HWCVD (P-HWCVD) was used to prepare poly-crystalline silicon (poly-Si) thin films. The effects of the plasma on the film properties were studied by varying the RF power (P_w) from 0 to 40 W. The results indicate that, compared with that of HWCVD samples, the film crystalline fraction (X_c) is enhanced at low P_w assistance, whereas it decreases at higher P_w. The uniformity of the film thickness is considerably improved by introducing plasma. It is also found that the porosity of the film, indirectly detected from infrared spectra, is much reduced. Auger analysis of the tantalum filament used in the P-HWCVD process shows much lower silicon contamination than that in HWCVD.     

Growth of epitaxial sodium-bismuth-titanate films by metal-organic chemical vapor phase deposition

The liquid-delivery spin metal-organic chemical vapor phase deposition method was used to grow epitaxial sodium-bismuth-titanate films of the system Bi₄Ti₃O₁₂ + xNa_0.5Bi_0.5TiO₃ on SrTiO₃(001) substrates. Na(thd), Ti(OⁱPr)₂(thd)₂ and Bi(thd)₃, solved in toluene, were applied as source materials. Depending on the substrate temperature and the Na/Bi ratio in the gas phase several structural phases of sodium-bismuth-titanate were detected. With increasing temperature and/or Na/Bi ratio, phase transitions from an Aurivillius phase with m = 3 to m = 4 via an interleaved state with m = 3.5, and, finally, to Na_0.5Bi_0.5TiO₃ with perovskite structure (m = ∞) were established. These phase transitions proceed at remarkably lower temperatures than in ceramics or bulk crystals for which they had been exclusively observed so far.     

Impedance spectroscopy of manganite films prepared by metalorganic chemical vapor deposition

Polycrystalline Pr(1-x)CaxMnO3 (PCMO) films were prepared by liquid source metalorganic chemical vapor deposition using in situ infrared spectroscopic monitoring. The electric properties of the PCMO-based devices with Ni and Al electrodes (Ni-PCMO-Ni and Al-PCMO-Al devices) were studied by dc current-voltage (I-V) measurements and ac impedance spectroscopy. The current varied linearly with the applied voltage in Ni-PCMO-Ni devices, while nonlinear behavior was observed in I-V curves for Al-PCMO-Al devices. Impedance spectra were also different between Ni-PCMO-Ni and Al-PCMO-Al devices. The Cole-Cole plots for the Ni-PCMO-Ni devices showed only a single semicircular arc, which was assigned to the PCMO bulk impedance. Impedance spectra for the Al-PCMO-Al devices had two distinct components, which could be attributed to the PCMO bulk and to the interface between the PCMO film and the Al electrode, respectively. The bias dependence of the impedance spectra suggested that the resistance switching in the Al-PCMO-Al devices was mainly due to the resistance change in the interface between the film and the electrode. The metal electrode plays an important role in the resistance switching in the PCMO-based devices. The choice of the optimum metal electrodes is essential to the ReRAM application of the manganite-based devices.