In this work, we have designed a novel gas inlet structure for efficient usage of growth and doping precursors. Our previous gas injection configuration is that the gas is mixed to one pipe first, then divided into two pipes, and finally entered the chamber symmetrically above the substrate without a jet nozzle. The distance between gas inlet and substrate is about 14.75 cm. Our new design is to add a new tube in the center of the susceptor, and the distance between the new tube and substrate is about 0.5 cm. In this new design, different gas injection configurations have been planned such that the gas flow in the reactor aids the transport of reaction species toward the sample surface, expecting the utilization efficiency of the precursors being improved in this method. Experiments have shown that a high doping efficiency and fast growth could be achieved concurrently in diamond growth when methane and diborane come from this new inlet, demonstrating a successful implementation of the design to a diamond microwave plasma chemical vapor deposition system. Compared to our previous gas injection configuration, the growth rate increases by 15-fold and the boron concentration increases by ~ 10 times. COMSOL simulation has shown that surface reaction and precursor supply both have a change in determining the growth rate and doping concentration. The current results could be further applied to other dopants for solving the low doping efficiency problems in ultra-wide-band-gap semiconductor materials.
β-Ga2O3 has become the focus of considerable attention as an ultra-wide bandgap semiconductor following the successful development of bulk single crystals using the melt growth method. Accordingly, homoepitaxy studies, where the interface between the substrate and the epilayer is not problematic, have become mainstream and many results have been published. However, because the cost of homo-substrates is high, research is still mainly at the laboratory level and has not yet been scaled up to commercialization. To overcome this problem, many researchers are trying to grow high quality Ga2O3 epilayers on hetero-substrates. We used diluted SiH4 gas to control the doping concentration during the heteroepitaxial growth of β-Ga2O3 on c-plane sapphire using metal organic chemical vapor deposition (MOCVD). Despite the high level of defect density inside the grown β-Ga2O3 epilayer due to the aggregation of random rotated domains, the carrier concentration could be controlled from 1 × 1019 to 1 × 1016 cm-3 by diluting the SiH4 gas concentration. This study indicates that β-Ga2O3 hetero-epitaxy has similar potential to homo-epitaxy and is expected to accelerate the commercialization of β-Ga2O3 applications with the advantage of low substrate cost.
As the demand for p-type semiconductors increases, much effort is being put into developing new p-type materials. This demand has led to the development of novel new p-type semiconductors that go beyond existing p-type semiconductors. Copper iodide (CuI) has recently received much attention due to its wide band gap, excellent optical and electrical properties, and low temperature synthesis. However, there are limits to its use as a semiconductor material for thin film transistor devices due to the uncontrolled generation of copper vacancies and excessive hole doping. In this work, p-type CuI semiconductors were fabricated using the chemical vapor deposition (CVD) process for thin-film transistor (TFT) applications. The vacuum process has advantages over conventional solution processes, including conformal coating, large area uniformity, easy thickness control and so on. CuI thin films were fabricated at various deposition temperatures from 150 to 250 °C The surface roughness root mean square (RMS) value, which is related to carrier transport, decreases with increasing deposition temperature. Hall effect measurements showed that all fabricated CuI films had p-type behavior and that the Hall mobility decreased with increasing deposition temperature. The CuI TFTs showed no clear on/off because of the high concentration of carriers. By adopting a Zn capping layer, carrier concentrations decreased, leading to clear on and off behavior. Finally, stability tests of the PBS and NBS showed a threshold voltage shift within ±1 V.
Large-area graphene of the order of centimeters was deposited on copper substrates by low-pressure chemical vapor deposition (LPCVD) using hexane as the carbon source. The effect of temperature and the carrier gas flowrates on the quality and uniformity of the as-deposited graphene was investigated using the Raman analysis. The film deposited at 870 °C with a total carrier gas flowrate of 50 sccm is predominantly single-layer with very low defects according to the Raman spectra. The 2D/G peak intensity ratios obtained from the Raman spectra of samples from three different locations of graphene deposited on a whole copper catalyst was used to calculate the large-area uniformity. Based on the results, a very high uniformity of 89.6% was calculated for the graphene deposited at 870 °C. The uniformity was observed to decrease with increasing temperature. Similar to the thickness uniformity, the electrical conductivity values obtained as a result of I–V measurements and water contact angle measurements were found to be close to each other for the graphene deposited under the same deposition conditions.
In this study, graphene was rapidly grown by chemical vapor deposition using a liquid cell for supplying methanol as a carbon source of graphene. To realize the rapid growth, methanol which is carbon-contained organic solvent was used instead of methane gas, a widely used carbon source for graphene growth. The graphene grown with the growth time as a variable was transferred to a SiO2/ Si substrate with an oxide thickness of 300 nm to confirm whether it was grown with full coverage with an optical microscope. The results confirmed a full coverage in 0.5 min of growth. The Raman spectra also confirmed the G-peak position at 1585.0 cm−1 and an intensity ratio of 2D/G at 2.3 or higher. Concerning electrical transport characteristics, at an induced carrier density of 1 × 1012 cm−2, the hole (μh) and electron (μe) mobilities were 1524 cm2 V−1 s−1 and 1528 cm2 V−1 s−1, respectively. Thus, our study confirmed that high-quality, large-area graphene can be grown within 0.5 min.
Continuous synthesis of high-crystalline carbon nanotubes (CNTs) is achieved by reconfiguring the injection part in the reactor that is used in the floating catalyst chemical vapor deposition (FC-CVD) process. The degree of gas mixing is divided into three cases by adjusting the configuration of the injection part: Case 1: most-delayed gas mixing (reference experiment), Case 2: earlier gas mixing than Case 1, Case 3: earliest gas mixing. The optimal synthesis condition is obtained using design of experiment (DOE) in the design of Case 1, and then is applied to the other cases to compare the synthesis results. In all cases, the experiments are performed by varying the timing of gas mixing while keeping the synthesis conditions constant. Production rate (Case 1: 0.63 mg/min, Case 2: 0.68 mg/min, Case 3: 1.29 mg/min) and carbon content (Case 1: 39.6 wt%, Case 2: 57.1 wt%, Case 3: 71.6 wt%) increase as the gas-mixing level increases. The amount of by-products decreases stepwise as the gas-mixing level increases. The IG/ID ratio increases by a factor of 7 from 10.3 (Case 1) to 71.7 (Case 3) as the gas-mixing level increases; a high ratio indicates high-crystalline CNTs. The radial breathing mode (RBM) peak of Raman spectrograph is the narrowest and sharpest in Case 3; this result suggests that the diameter of the synthesized CNTs is the most uniform in Case 3. This study demonstrates the importance of configuration of the injection part of the reactor for CNT synthesis using FC-CVD.
The study presented in the article is focused on use of graphene obtained by novel microwave-enhanced chemical vapor deposition (MECVD) method as a construction material for 3D porous structures—aerogels and sponges. MECVD graphene nanoplatelets-based aerogels were obtained by mixing MECVD graphene nanoplatelets and chitosan, dissolved in 3% acetic acid followed by its freeze drying and carbonization at 800° in inert medium. Surface morphology of aerogels was characterized by SEM. MECVD graphene nanoplatelets-based aerogels are characterized by a porous structure; they are superhydrophobic and possess high sorption capacity with regard to organic liquids of different densities. Polyurethane sponges coated with MECVD graphene can serve as an alternative to aerogels. The process of their obtaining is cheaper and less complicated. They were obtained by facile “dip-coating” method, modifying its surface to increase its hydrophobicity. The resulting sponges are superhydrophobic and superoleophilic, and demonstrate high rate of sorption of organic liquids and can be easily regenerated by squeezing. In addition, they can be used as a separating material in conjunction with vacuum system for continuous and selective collection of organic liquids from the surface of water.
In this study, an empirical relationship between the energy band gap of multi-walled carbon nanotubes (MWCNTs) and synthesis parameters in a chemical vapor deposition (CVD) reactor using factorial design of experiment was established. A bimetallic (Fe-Ni) catalyst supported on CaCO3 was synthesized via wet impregnation technique and used for MWCNT growth. The effects of synthesis parameters such as temperature, time, acetylene flow rate, and argon carrier gas flow rate on the MWCNTs energy gap, yield, and aspect ratio were investigated. The as-prepared supported bimetallic catalyst and the MWCNTs were characterized for their morphologies, microstructures, elemental composition, thermal profiles and surface areas by high-resolution scanning electron microscope, high resolution transmission electron microscope, energy dispersive X-ray spectroscopy, thermal gravimetry analysis and Brunauer-Emmett-Teller. A regression model was developed to establish the relationship between band gap energy, MWCNTs yield and aspect ratio. The results revealed that the optimum conditions to obtain high yield and quality MWCNTs of 159.9% were: temperature (700ºC), time (55 min), argon flow rate (230.37 mL min–1) and acetylene flow rate (150 mL min–1) respectively. The developed regression models demonstrated that the estimated values for the three response variables; energy gap, yield and aspect ratio, were 0.246 eV, 557.64 and 0.82. The regression models showed that the energy band gap, yield, and aspect ratio of the MWCNTs were largely influenced by the synthesis parameters and can be controlled in a CVD reactor.
Membrane-based CO2 capture is an energy-saving way to separate CO2 from N2 in post-combustion. Chabazite (Si-CHA) zeolites with a pore size of 0.37 nm × 0.42 nm are expected to separate CO2 from larger N2 (0.364 nm) by recognizing minute size differences. The pore mouth size on the Si-CHA zeolites outer surface was reduced via the chemical vapor deposition (CVD) to increase the molecular sieving effect by disfavoring the penetration of N2. The CVD process was conducted on CHA membranes to improve their CO2/N2 separation performance. Compared to the intact CHA membranes, the CO2/N2 max separation factor for CVD-treated CHA membranes increased by ~2.5 fold under dry conditions and by ~6.4 fold under wet conditions. It is noteworthy that the membrane kept its separation performance without degradation in the presence of H2O.
Cobalt was electrodeposited onto chemical vapor deposition (CVD) graphene/Si/SiO2 substrates, during different time intervals, using an electrolyte solution containing a low concentration of cobalt sulfate. The intention was to investigate the details of the deposition process (and the dissolution process) and the resulting magnetic properties of the Co deposits on graphene. During and after electrodeposition, in-situ magnetic measurements were performed using an (AGFM). These were followed by ex situ morphological analysis of the samples with ΔtDEP 30 and 100 s by atomic force microscopy in the non-contact mode on pristine CVD graphene/SiO2/Si. We demonstrate that it is possible to electrodeposit Co onto graphene, and that in-situ magnetic measurements can also help in understanding details of the deposition process itself. The results show that the Co deposits are ferromagnetic with decreasing coercivity (HC) and demonstrate increasing magnetization on saturation (MSAT) and electric signal proportional to remanence (Mr), as a function of the amount of the electrodeposited Co. It was also found that, after the end of the dissolution process, a certain amount of cobalt remains on the graphene in oxide form (this was confirmed by X-ray photoelectron spectroscopy), as suggested by the magnetic measurements. This oxide tends to exhibit a limited asymptotic amount when cycling through the deposition/dissolution process for increasing deposition times, possibly indicating that the oxidation process is similar to the graphene surface chemistry.
Graphene was grown on molybdenum (Mo) foil by a chemical vapor deposition method at different growth temperatures (1000°C, 1100°C, and 1200°C). The properties of graphene were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy, and Raman spectroscopy. The results showed that the quality of the deposited graphene layer was affected by the growth temperature. XRD results showed the presence of a carbide phase on the Mo surface; the presence of carbide was more intense at 1200°C. Additionally, a higher I2D/IG ratio (0.418) was observed at 1200°C, which implies that there are fewer graphene layers at this temperature. The lowest ID/IG ratio (0.908) for the graphene layers was obtained at 1200°C, suggesting that graphene had fewer defects at this temperature. The size of the graphene domains was also calculated. We found that by increasing the growth temperature, the graphene domain size also increased.
In this study, titanium(Ti) meshes and porous bodies are employed to synthesize carbon nanotubes(CNTs) using methane(CH4) gas and camphene solution, respectively, by chemical vapor deposition. Camphene is impregnated into Ti porous bodies prior to heating in a furnace. Various microscopic and spectroscopic techniques are utilized to analyze CNTs. It is found that CNTs are more densely and homogeneously populated on the camphene impregnated Ti-porous bodies as compared to CNTs synthesized with methane on Ti-porous bodies. It is elucidated that, when synthesized with methane, few CNTs are formed inside of Ti porous bodies due to methane supply limited by internal structures of Ti porous bodies. Ti-meshes and porous bodies are found to be multi-walled with high degree of structural disorders. These CNTs are expected to be utilized as catalyst supports in catalytic filters and purification systems.
A zinc oxide (ZnO) hybrid structure was successfully fabricated on a glass substrate by metal organic chemical vapor deposition (MOCVD). In-situ growth of a multi-dimensional ZnO hybrid structure was achieved by adjusting the growth temperature to determine the morphologies of either film or nanorods without any catalysts such as Au, Cu, Co, or Sn. The ZnO hybrid structure was composed of one-dimensional (1D) nanorods grown continuously on the two-dimensional (2D) ZnO film. The ZnO film of 2D mode was grown at a relatively low temperature, whereas the ZnO nanorods of 1D mode were grown at a higher temperature. The change of the morphologies of these materials led to improvements of the electrical and optical properties. The ZnO hybrid structure was characterized using various analytical tools. Scanning electron microscopy (SEM) was used to determine the surface morphology of the nanorods, which had grown well on the thin film. The structural characteristics of the polycrystalline ZnO hybrid grown on amorphous glass substrate were investigated by X-ray diffraction (XRD). Hall-effect measurement and a four-point probe were used to characterize the electrical properties. The hybrid structure was shown to be very effective at improving the electrical and the optical properties, decreasing the sheet resistance and the reflectance, and increasing the transmittance via refractive index (RI) engineering. The ZnO hybrid structure grown by MOCVD is very promising for opto-electronic devices as Photoconductive UV Detectors, anti-reflection coatings (ARC), and transparent conductive oxides (TCO).
Exceptional progress has been made with chemical vapor deposition (CVD) of graphene in the past few years. Not only has good monolayer growth of graphene been achieved, but large-area synthesis of graphene sheets has been successful too. However, the polycrystalline nature of CVD graphene is hampering further progress as graphene property degrades due to presence of grain boundaries. This review will cover factors that affect nucleation of graphene and how other scientists sought to obtain large graphene domains. In addition, the limitation of the current research trend will be touched upon as well.
High-quality β-silicon carbide (SiC) coatings are expected to prevent the oxidation degradation of carbon fibers in carbon fiber/silicon carbide (C/SiC) composites at high temperature. Uniform and dense β-SiC coatings were deposited on carbon fibers by low-pressure chemical vapor deposition (LP-CVD) using silane (SiH4) and acetylene (C2H2) as source gases which were carried by hydrogen gas. SiC coating layers with nanometer scale microstructures were obtained by optimization of the processing parameters considering deposition mechanisms. The thickness and morphology of β-SiC coatings can be controlled by adjustment of the amount of source gas flow, the mean velocity of the gas flow, and deposition time. XRD and FE-SEM analyses showed that dense and crack-free β-SiC coating layers are crystallized in β-SiC structure with a thickness of around 2 micrometers depending on the processing parameters. The fine and dense microstructures with micrometer level thickness of the SiC coating layers are anticipated to effectively protect carbon fibers against the oxidation at high-temperatures.
We report a highly sensitive NO2 gas sensor based on multi-layer graphene (MLG) films synthesized by a chemical vapor deposition method on a microheater-embedded flexible substrate. The MLG could detect low-concentration NO2 even at sub-ppm (<200 ppb) levels. It also exhibited a high resistance change of ~6% when it was exposed to 1 ppm NO2 gas at room temperature for 1 min. The exceptionally high sensitivity could be attributed to the large number of NO2 molecule adsorption sites on the MLG due to its a large surface area and various defect-sites, and to the high mobility of carriers transferred between the MLG films and the adsorbed gas molecules. Although desorption of the NO2 molecules was slow, it could be enhanced by an additional annealing process using an embedded Au microheater. The outstanding mechanical flexibility of the graphene film ensures the stable sensing response of the device under extreme bending stress. Our large-scale and easily reproducible MLG films can provide a proof-of-concept for future flexible NO2 gas sensor devices.
The electrical and optical properties of fluorine-doped tin oxide films grown on polyethylene terephthalate film witha hardness of 3 using electron cyclotron resonance plasma with linear microwave of 2.45GHz of high ionization energy wereinvestigated. Fluorine-doped tin oxide films with a magnetic field of 875 Gauss and the highest resistance uniformity wereobtained. In particular, the magnetic field could be controlled by varying the distribution in electron cyclotron depositionpositions. The films were deposited at various gas flow rates of hydrogen and carrier gas of an organometallic source. Thesurface morphology, electrical resistivity, transmittance, and color in the visible range of the deposited film were examined usingSEM, a four-point probe instrument, and a spectrophotometer. The electromagnetic field for electron cyclotron resonancecondition was uniformly formed in at a position 16cm from the center along the Z-axis. The plasma spatial distribution ofmagnetic current on the roll substrate surface in the film was considerably affected by the electron cyclotron systems. Therelative resistance uniformity of electrical properties was obtained in film prepared with a magnetic field in the current rangeof 180~200A. SEM images showing the surface morphologies of a film deposited on PET with a width of 50cm revealedthat the grains were uniformly distributed with sizes in the range of 2~7nm. In our experimental range, the electrical resistivityof film was able to observe from 1.0×10−2 to 1.0×10−1Ωcm where optical transmittance at 550nm was 87~89%. Theseproperties were depended on the flow rate of the gas, hydrogen and carrier gas of the organometallic source, respectively.
We investigated the effects of parametric synthesis conditions of catalysts such as sintering temperature, sorts of supports and compositions of catalysts on alignment and length-control of carbon nanotubes (CNTs) using catalyst powders. To obtain aligned CNTs, several parameters were changed such as amount of citric acid, calcination temperature of catalysts, and the sorts of supports using the combustion method as well as to prepare catalyst. CNTs with different lengths were synthesized as portions of molybdenum and iron using a chemical vapor deposition reactor. In this work, the mechanisms of alignment of CNTs and of the length-control of CNTs are discussed.
Graphene has been synthesized on 100- and 300-nm-thick Ni/SiO2/Si substrates with CH4 gas (1 SCCM) diluted in mixed gases of 10% H2 and 90% Ar (99 SCCM) at 900˚C by using inductively-coupled plasma chemical vapor deposition (ICP-CVD). The film morphology of 100-nm-thick Ni changed to islands on SiO2/Si substrate after heat treatment at 900˚C for 2 min because of grain growth, whereas 300-nm-thick Ni still maintained a film morphology. Interestingly, suspended graphene was formed among Ni islands on 100-nm-thick Ni/SiO2/Si substrate for the very short growth of 1 sec. In addition, the size of the graphene domains was much larger than that of Ni grains of 300-nm-thick Ni/SiO2/Si substrate. These results suggest that graphene growth is strongly governed by the direct formation of graphene on the Ni surface due to reactive carbon radicals highly activated by ICP, rather than to well-known carbon precipitation from carbon-containing Ni. The D peak intensity of the Raman spectrum of graphene on 300-nm-thick Ni/SiO2/Si was negligible, suggesting that high-quality graphene was formed. The 2D to G peak intensity ratio and the full-width at half maximum of the 2D peak were approximately 2.6 and 47cm-1, respectively. The several-layer graphene showed a low sheet resistance value of 718Ω/sq and a high light transmittance of 87% at 550 nm.