Catalytic-free growth of ZnGa2O4 nanowires on amorphous carbon layers

Zinc gallate (ZnGa₂O₄) nanowires were directly grown on the amorphous carbon-coated silicon substrates using a facile chemical vapor deposition method without any metal catalysts. The growth mechanism can be attributed to a self-organization vapor-liquid-solid (VLS) process. The amorphous carbon layer plays an important role in the nucleation and growth process of the ZnGa₂O₄ nanowires. The photoluminescence (PL) of the nanowires shows a broad, strong green emission band centered at 532 nm and a weak UV emission band at 381 nm, which can be attributed to a large amount of ionized oxygen vacancies and the combination of Ga³⁺ ions with free electrons in coordinated oxygen vacancies, respectively.     

Growth of single-walled carbon nanotube arrays from samarium on substrates

In this letter, it is reported for the first time that samarium is an effective catalyst for single-walled carbon nanotubes(SWNTs) growth via a chemical vapor deposition(CVD) process. Horizontally superlong well-oriented SWNT arrays can be generated under suitable conditions by using ethanol as carbon source. The single-wall structure was characterized by scanning electron microscopy, Raman spectroscopy and atomic force microscopy. The results show that the SWNTs from samarium have better conductivity and better structural uniformity with less defects. This rare earth metal element provides not only an alternative catalyst for SWNTs growth but also a possible way to generate high percentage of superlong semiconducting SWNT arrays for various applications of nanoelectronic device.     

Structural and optical properties of Al-doped SnO2 nanowires

We report a facile thermal evaporation method for the syntheses of Al-doped SnO₂ nanowires using Al-doped SnO₂ nanoparticles as precursors. High-density, single-crystalline Al-doped SnO₂ nanowires were directly grown on the 6H-SiC substrates without any catalyst. X-ray diffraction patterns show that the Al dopants are incorporated into the rutile SnO₂ nanowires. The X-ray photoelectron spectra confirm the SnO₂ nanowires doped with 5 at.% Al. The photoluminescence spectra of the Al-doped SnO₂ nanowires exhibit that the large blue shift of the emission band can be observed in the Al-doped SnO₂ nanowires compared with undoped nanowires. The distortion of the crystal lattices caused by incorporation of Al atoms at the interstitials should be responsible for the large blue shift of the emission band.     

Synthesis of carbon nanofibers using C60, graphite and boron

The growth of carbon nanofibers (CNFs) using C₆₀, graphite-carbon and boron powders via the ultrasonic spray pyrolysis method of ethanol is reported. CNFs of various morphologies were observed with different powders. Kinked CNFs of about 100 nm were produced while using a mixture of C₆₀ particles and ethanol as precursors, whereas straight CNFs were obtained using graphite-carbon and boron powders as catalysts. Element analysis measurement of the as-produced CNFs shows that the CNFs synthesized using C₆₀ and graphite powder have the carbon particles on the tip. When boron powders were added in ethanol, boron related materials were examined at the tip of the CNFs. The present study indicates that the clusters composed of carbon and boron related materials act as nucleating sites for CNF formation.     

碳纳米管阵列/热解炭复合材料的制备和表征（英文）

以甲烷为碳源,通过化学气相沉积和化学蒸汽渗透两步法将热解炭填充至碳纳米管阵列间的空隙而制备出碳纳米管阵列/热解炭复合材料。采用扫描电镜和拉曼光谱仪对样品的结构进行表征。结果表明,碳纳米管被热解炭填充和覆盖形成均相的复合膜,其密度增加4倍,同时热解炭已石墨化。     

Ultrahigh density modulation of aligned single-walled carbon nanotube arrays

Controlling the densities of aligned single-walled carbon nanotube arrays (SWNTs) on ST-cut quartz is a critical step in various applications of these materials. However the growth mechanism for tuning SWNT density using the chemical vapor deposition (CVD) method is still not well understood, preventing the development of efficient ways to obtain the desired results. Here we report a general “periodic” approach that achieves ultrahigh density modulation of SWNT arrays on ST-cut quartz substrates—with densities increased by up to ∼60 times compared with conventional methods using the same catalyst densities—by varying the CH₄ gas “off” time. This approach is applicable to a wide range of initial catalyst densities, substrates, catalyst types and growth conditions. We propose a general mechanism for the catalyst size-dependent nucleation of SWNTs associated with different free carbon concentrations, which explains all the observations. Moreover, the validity of the model is supported by systematic experiments involving the variation of key parameters in the “periodic” CVD approach.      

Diameter dependent growth mode of carbon nanotubes on nanoporous SiO2 substrates

Two different growth modes of carbon nanotubes (CNTs) are identified in ethylene chemical vapour deposition (CVD) using SiO₂ as support. With a series of electron microscopy observations, we have found that small-diameter nanotubes favor a root-growth mechanism on nanoporous SiO₂ support, while nanotubes with larger diameters prefer a tip-growth. The dependence of growth mode on tube diameter is explained in terms of the porosity of the support and the size distribution of the catalyst. Our results provide clues to control growth of CNTs and obtain well-organized nanotube structures.     

Preparation and electrochemical properties of nitrogen-doped multi-walled carbon nanotubes

High yield bamboo-shaped N-doped multi-walled carbon nanotubes (MWNTs), containing 2.27 at.% N, were fabricated by pyrolysis of pyridine at 800 °C in an Ar atmosphere. The electrochemical capacitive performances of this type of carbon fiber were evaluated in 6 M KOH aqueous solution. The specific capacitance of N-doped MWNT electrode is measured to be 44.3 F/g at the charge/discharge current of 1 mA, which is two times greater than that of the undoped one (19.9 F/g). The measurements also reveal that the N-doped MWNT electrode possesses lower equivalent series resistance (0.24 Ω) and higher knee frequency (1995 Hz) than the undoped one. This improvement is attributed to the unique morphology and electronic properties of N-doped MWNTs.     

Catalyst-free growth of oriented single-walled carbon nanotubes on mica by ethanol chemical vapor deposition

In this letter, it is reported for the first time that single-walled carbon nanotubes (SWNTs) can grow on mica substrate without additional catalyst by chemical vapor deposition (CVD) using ethanol as carbon source. The single-wall structure was characterized by Raman spectra and AFM (Atomic Force Microscopy) measurements. The growth of carbon nanotubes on mica surface contributes to the small amount of iron oxide in bare mica. The uniform dispersion and nanosized Fe particles formed from the reduction of iron oxide favor for the growth of SWNTs. Horizontally aligned superlong SWNTs arrays can be successfully generated on the mica surface, which is proved to be guided by the gas flow and under “kite growth mechanism”. The mica is a machinable material which can be easily cut and made a narrow slit on, thus the nanotubes can traverse the slit which can be in millimeter scale and long suspended SWNTs can be generated. This will provide an opportunity to manipulate individual SWNT for various purposes.     

Silicon nanowires grown from copper oxalate

Si nanowires (SiNWs) have been synthesized facilely from products in the thermal decomposition of copper oxalate in a chemical vapor deposition (CVD) system by the vapor-solid-solid (VSS) mechanism. Raman investigations showed that the phonon confinement appeared in the grown SiNWs. We found the mechanism of catalyst formation to be that the initial copper oxalate micro balls were thermally decomposed to fabricate Cu and Cu₂O nanoparticles, which reacted with silane sequentially to form Cu₃Si, serving as the nuclei for the sequential VSS growth of SiNWs.     

Characteristics of carbon coatings on optical fibers prepared by radio-frequency plasma enhanced chemical vapor deposition with different H2/C2H2 ratios

Characteristics of carbon coatings on optical fibers prepared by radio-frequency plasma enhanced chemical vapor deposition with different H₂/C₂H₂ ratios are investigated. Five kinds of carbon coatings are prepared with H₂/C₂H₂ ratios of 2, 4, 6, 8, and 10. Experimental results show that the deposition rate and surface roughness of carbon coatings decrease as the H₂/C₂H₂ ratio increases. When the H₂/C₂H₂ ratio changes from 2 to 8, the increase of H₂/C₂H₂ ratios detrimentally yields sp³ carbon atoms and sp³-CH₃ bonds in the carbon coatings. However, when the H₂/C₂H₂ ratio exceeds 8, the hydrogen retards the growth of the graphite structure. Moreover, the redundant hydrogen radicals favor bonding with the dangling bonds in the coating surface. Therefore, when the H₂/C₂H₂ ratio increases from 8 to 10, the amounts of sp³ carbon atoms and sp³-CH₃ bonds in the carbon coatings increase. At an H₂/C₂H₂ ratio of 8, the carbon coating exhibits excellent water-repellency and thermal-loading resistance, and so this ratio is the best for producing a hermetically sealed optical fiber coating.     

In situ growth carbon nanotube reinforced SiCf/SiC composite

Carbon nanotube (CNT) reinforced SiC_f/SiC composite was prepared by in situ chemical vapor deposition (CVD) growth of CNTs on SiC fibers then following polymer impregnation pyrolysis (PIP) process. The nature of CNTs and the microstructure of the as prepared CNT-SiC_f/SiC composite were investigated. The mechanical properties of the as prepared CNT-SiC_f/SiC composite were measured. The results reveal that the in situ CVD growth of CNTs on SiC fibers remarkably promotes the mechanical properties of SiC_f/SiC composite. The secondly pull-out of CNTs from matrix during the pull-out of the SiC fibers from matrix consumes the deformation energies, resulting in promotion of the mechanical properties for composite.     

Tunable field emission properties of carbon nanotube arrays by engineering Fe catalysts

High-quality carbon nanotube (CNT) arrays composed of nanotubes with different diameters and wall numbers were synthesized by water-assisted chemical vapor deposition (CVD) from engineered Fe catalysts. Interestingly, the distribution of nanotube diameter and wall number broadened over 2.5 times as the catalytic Fe thickness increased. The mean diameter and wall number of nanotubes increased monotonically with the Fe thickness, while the calculated CNT area density within an array dropped about 32 times. Field emission measurements revealed that the turn-on voltage for CNT arrays decreased from 3.5 to 2.5 V/µm with the increased catalytic Fe thickness. It was believed that the screening effect from the proximity of neighboring nanotubes has a dominant influence than the CNT diameter on the resulting turn-on voltage.     

Designing a strategy for fabrication of single-walled carbon nanotube via CH4/N2 gas by the chemical vapor deposition method

Fe/Mo catalysts supported on alumina are suggested for the growth of single-walled carbon nanotubes (SWCNTs) by chemical vapor deposition (CVD) in methane (CH₄). One obvious synergistic advantage identified by molybdenum (Mo) is that by controlling the reaction temperature, it eliminates the need to activate the catalyst in hydrogen gas (H₂). So as activation of the growth catalyst in H₂ is a costly and extra step in the CVD method, this is a significant result of the present study. Herein, the sample quality and the dependence of carbon mass yield on CVD growth conditions are disserted. The activity of the catalyst is perused in the form of oxide under CH₄ flow (160 sccm) and in the temperature range of 680 to 1000 °C. We came to the conclusion that the Fe/Mo/Al₂O₃ oxide catalyst is activated at temperatures as low as 800 °C. Under these conditions (800 °C, 160 sccm of CH₄), the temperature is not enough for the tube to grow, but by increasing it, the desired conditions can be achieved (900 –1000 °C).     

Multi-walled carbon nanotube growth on oxidized silicon substrates using cyclohexane precursor by chemical vapor deposition

Randomly oriented multi-walled nanotubes (MWNTs) are grown by a thermal chemical vapor deposition (CVD) process from cyclohexane precursor on a 20% copper-80% nickel (Cu-Ni) catalyst on oxidized silicon substrates. This combination of precursor and catalyst, to our knowledge, has been employed for the first time to demonstrate growth of multi-walled carbon nanotubes. The effects of annealing, gas ambient and catalyst layer thickness on the morphology of the grown carbon layers are discussed. The low resistivity values of the MWNTs grown on oxidized silicon substrates are attractive for their potential use in photonic devices and display applications.     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.     

Field-emission characteristics of diamond-like amorphous carbon films deposited by mixed gas (N2 or H2) controlled i-C4H10 supermagnetron plasma

Diamond-like amorphous carbon (DAC) films were deposited for field-emission application using supermagnetron plasma by mixing N₂ or H₂ in i-C₄H₁₀ gas at the upper and lower electrode rf powers (UPRF/LORF) of 800 W/100-800 W. At an 800 W/800 W, the N₂ (0-80%) gas-mixed DAC films showed an emission threshold electric field (E_TH) of 19 V/μm. At the 800 W/100 W, the H₂ (20%) gas-mixed DAC film showed low E_TH's of 13 V/μm, respectively. The moderate reduction of CC and CN double bonds by the decrease of LORF from 800 W to 100 W was found to be effective to lower E_TH.     

Fabrication and electrochemical behavior of single-walled carbon nanotube/graphite-based electrode

An electrochemical method for determining the dihydroxybenzene derivatives on glassy carbon (GC) has been developed. In this method, the performance of a single-walled carbon nanotube (SWCNT)/graphite-based electrode, prepared by mixing SWCNTs and graphite powder, was described. The resulting electrode shows an excellent behavior for redox of 3,4-dihydroxybenzoic acid (DBA). SWCNT/graphite-based electrode presents a significant decrease in the overvoltage for DBA oxidation as well as a dramatic improvement in the reversibility of DBA redox behavior in comparison with graphite-based and glassy carbon (GC) electrodes. In addition, scanning electron microscopy (SEM) and atomic force microscopy (AFM) procedures performed for used SWCNTs.     

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.     

Mo-Co catalyst nanoparticles: Comparative study between TiN and Si surfaces for single-walled carbon nanotube growth

Highly pure single-walled carbon nanotubes (SWNT) were synthesized by alcohol catalytic chemical vapor deposition on silicon substrates partially covered by a thin layer of TiN. The TiN coating selectively prevented the growth of carbon nanotubes. Field emission scanning electron microscopy and Raman spectroscopy revealed the formation of high purity vertically aligned SWNT in the Si region. X-ray Photoelectron Spectroscopy and Atomic Force Microscopy indicated that Co nanoparticles are present on the Si regions, and not on the TiN regions. This clearly explains the obtained experimental results: the SWNT only grow where the Co is presented as nanoparticles, i.e. on the Si regions.