Synthesis of carbon-mineral composites and graphene

Abstract

С/Al₂O₃ and C/MgO carbon-mineral composites were synthesized by propane decomposition over Al₂O₃ at 600–650?°C and MgO carbonization in 1,3-butadiene at 600?°C. The synthesized carbon-mineral composites were studied by EPR, XRD and transmission electron microscopy. It was found that a mosaic structure of carbon clusters was formed on the internal surface of the oxides and gradually grew until it covered its whole surface. A method for synthesis of graphene materials by using MgO as a template followed by its dissolution in hydrochloric acid was suggested. A maximum was observed on the dependence of the graphene surface area on the carbon concentration in the composites. The highest specific surface area of the synthesized graphene about 1800–1900?m²/g was observed for the samples obtained from C-MgO composites containing 8–10?wt.% C.     

Growth of large-area single- and Bi-layer graphene by controlled carbon precipitation on polycrystalline Ni surfaces

We report graphene films composed mostly of one or two layers of graphene grown by controlled carbon precipitation on the surface of polycrystalline Ni thin films during atmospheric chemical vapor deposition (CVD). Controlling both the methane concentration during CVD and the substrate cooling rate during graphene growth can significantly improve the thickness uniformity. As a result, one- or two- layer graphene regions occupy up to 87% of the film area. Single layer coverage accounts for 5%–11% of the overall film. These regions expand across multiple grain boundaries of the underlying polycrystalline Ni film. The number density of sites with multilayer graphene/graphite (>2 layers) is reduced as the cooling rate decreases. These films can also be transferred to other substrates and their sizes are only limited by the sizes of the Ni film and the CVD chamber. Here, we demonstrate the formation of films as large as 1 in². These findings represent an important step towards the fabrication of large-scale high-quality graphene samples. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Hydrothermally grown ZnO nanostructures on few-layer graphene sheets

This study describes the hydrothermal growth of ZnO nanostructures on few-layer graphene sheets and their optical and structural properties. The ZnO nanostructures were grown on graphene sheets of a few layers thick (few-layer graphene) without a seed layer. By changing the hydrothermal growth parameters, including temperature, reagent concentration and pH value of the solution, we readily controlled the dimensions, density and morphology of the ZnO nanostructures. More importantly, single-crystalline ZnO nanostructures grew directly on graphene, as determined by transmission electron microscopy. In addition, from the photoluminescence and cathodoluminescence spectra, strong near-band-edge emission was observed without any deep-level emission, indicating that the ZnO nanostructures grown on few-layer graphene were of high optical quality.     

Synthesis of large-area, few-layer graphene on iron foil by chemical vapor deposition

We demonstrate a simple and controllable way to synthesize large-area, few-layer graphene on iron substrates by an optimized chemical vapor deposition (CVD) method using a mixture of methane and hydrogen. Based on an analysis of the Fe-C phase diagram, a suitable procedure for the successful synthesis of graphene on Fe surfaces was designed. An appropriate temperature and cooling process were found to be very important in the synthesis of highly crystalline few-layer graphene. Graphene-based field-effect transistor (FET) devices were fabricated using the resulting few-layer graphene, and showed good quality with extracted mobilities of 300–1150 cm²/(V·s).      

Novel ZnO nanostructures grown on carbon nanotubes by thermal evaporation

We report on the formation of ZnO/carbon nanotubes heterostructures achieved by means of a thermal evaporation method. Scanning electron microscopy revealed that the main building block of the observed morphologies was the nanorod whose self-assembling resulted in various structures such as polypods and nano-hedgehogs, depending on various factors as well as the location of the ZnO-CNT junction. X-ray diffraction and photoluminescence spectroscopy were used to study the structure and optical properties of obtained nanostructures. Semi-empirical molecular orbital calculations gave evidence for the nature of the binding between ZnO and CNTs.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Layer-by-layer growth of graphene layers on graphene substrates by chemical vapor deposition

We demonstrate a synthesis of graphene layers on graphene templates prepared by the mechanical exfoliation of graphite crystals using a developed chemical vapor deposition (CVD) apparatus that has a furnace with three temperature zones and can regulate the temperatures separately in each zone. This results in individual control over the decomposition reaction of the carbon feedstock and the growth of graphene layers by activated carbon species. CVD growth using multi-temperature zones provides wider temperature windows appropriate to grow graphene layers. We observed that graphene layers proceed by a layer-by-layer growth mode using an optical microscopy, an atomic force microscopy, and Raman spectroscopy. This result suggests that a graphene growth technique using the CVD apparatus is a potential approach for making graphene sheets with precise control of the layer numbers.     

Nitrogen-doped carbon nanotube arrays grown on graphene substrate

Nitrogen-doped carbon nanotube (N-doped CNT) arrays have been synthesized on graphene substrate by chemical vapor deposition process, in which iron nanoparticles (NPs) assembled on the graphene sheet were generated in situ from the reduction of Fe₃O₄ NPs/reduced graphene oxide (RGO) and were used as catalyst. The morphology and structure of the N-doped CNT arrays were investigated by field emission scanning electron microscope and high-resolution transmission electron microscope. The N-doped CNTs were bamboo-shaped and the density can be controlled by modulating the density of catalyst NPs on RGO sheets. The concentration and incorporation of nitrogen were studied by elemental analysis, X-ray photoelectron spectroscope and Raman analysis, and the results showed that the nitrogen content was around 3 wt.%. Because of the good conductivity of graphene structure, N-doped CNT arrays grown on graphene substrate may be promising candidates as noble metal-free electrodes for oxygen reduction reaction in the future.     

ZnO nanostructures grown on epitaxial GaN

Presented is the growth of zinc oxide nanorod/nanowire arrays on gallium nitride epitaxial layers. A hierarchical zinc oxide morphology comprising of different scale zinc oxide nanostructures was observed. The first tier of the surface comprised of typical zinc oxide nanorods, with most bridging to adjacent nanorods. While the second tier comprised of smaller zinc oxide nanowires approximately 30 nm in width often growing atop the aforementioned bridges. Samples were analysed via scanning electron microscopy, as well as, cross-sectional and high resolution transmission electron microscopy to elucidate the detailed growth and structural elements of the heterostructure.     

Facile, noncovalent decoration of graphene oxide sheets with nanocrystals

Facile dry decoration of graphene oxide sheets with aerosol Ag nanocrystals synthesized from an arc plasma source has been demonstrated using an electrostatic force directed assembly technique at room temperature. The Ag nanocrystal-graphene oxide hybrid structure was characterized by transmission electron microscopy (TEM) and selected area diffraction. The ripening of Ag nanocrystals on a graphene oxide sheet was studied by consecutive TEM imaging of the same region on a sample after heating in Ar at elevated temperatures of 100 °C, 200 °C, and 300 °C. The average size of Ag nanocrystals increased and the number density decreased after the annealing process. In particular, migration and coalescence of Ag nanocrystals were observed at a temperature as low as 100 °C, suggesting a van der Waals interaction between the Ag nanocrystal and the graphene oxide sheet. The availability of affordable graphene-nanocrystal structures and their fundamental properties will open up new opportunities for nanoscience and nanotechnology and accelerate their applications. This article is published with open access at Springerlink.com     

Growth mechanism of ZnO nanostructures in wet-oxidation process

Zinc (Zn) thin films were prepared by direct current magnetron sputtering as precursors with different deposition times. Zinc oxide (ZnO) nanostructures such as nanowires, nanobelts and nanoblades were then synthesized from the Zn precursors by wet-oxidation process. The microstructures of the Zn precursor and ZnO nanostructures have been studied by scanning electronic microscopy and X-ray diffractometry. The optoelectronic properties were analyzed by photoluminescence measurement. It was found that the Zn precursor film with a porous top layer consisting of well-crystallized Zn grains is an essential for formation of ZnO nanowires. Along with time dependence study and temperature dependence studies, the ZnO nanostructure growth mechanisms during the wet-oxidation process are proposed: water vapor has a major influence on the initial stage, and the final dimensions of the nanostructure are controlled by the vapor-solid process.     

Improved physical properties of ZnO nanostructures by In inclusion

An alternative route to improve the physical properties of ZnO nanostructures has been demonstrated. With In inclusion in the growth process, we show that the morphology of ZnO nanostructures can be changed from nanopins to nanowires. Besides, the major effects of In inclusion involve the reduction of crystallization velocity, improvement of crystalline quality, and suppression of defect density. Notably, the emission intensity can be enhanced by more than one order of magnitude. Our result therefore provides an excellent approach to obtain good crystalline quality of nanometerials for the application of optoelectronic devices.     

High-quality hexagonal ZnO crystals grown by chemical vapor deposition

High-quality zinc oxide (ZnO) crystals were grown on a (0001) sapphire substrate by chemical vapor deposition at 830 °C under atmospheric pressure. The hexagonal crystals had an average diameter of about 150 μm, and a thickness of about 15 μm, as observed under a polarizing microscope. The large (0002) facet was flat, regular, and neat. In the X-ray diffraction pattern, strong (0002) and weak (0004) peaks indicate that the crystals had a wurtzite structure. The crystalline quality was characterized by Raman scattering, and the E₂(high), E₂(low), and A_l(LO) modes confirm the high quality of the ZnO crystals. Photoluminescence (PL) spectra of the crystals had a strong and sharp ultraviolet emission peak at 379 nm. The PL mechanism was also discussed.     

High quality epitaxial ZnO films grown on solid-phase crystallized buffer layers

High quality epitaxial ZnO films on sapphire (110) plane have been fabricated on ZnO homo-buffer layers crystallized via solid-phase epitaxially (SPE). The SPE-ZnO films are fabricated by annealing of amorphous ZnON (a-ZnON) films deposited by RF magnetron sputtering. During annealing, the a-ZnON films are oxidized and converted to ZnO crystal. X-ray diffraction (XRD) analysis shows that the resultant films are epitaxially grown on the sapphire substrates. By using the SPE-ZnO films as homo-buffer layers, the ZnO films with high crystallinity, which are deposited by RF magnetron sputtering, are fabricated. The full width at half-maximum of XRD patterns for 2θ-ω and ω scan of (002) plane are 0.094° and 0.12°, respectively, being significantly small compared with 0.24° and 0.55° for the films without buffer layers. Thus utilizing SPE buffer layers is very promising to obtain epitaxial ZnO films with high crystallinity.     

Annealing and partial pressure ratio effects on ZnO films grown by metal-organic chemical vapor deposition using tert-butanol as oxidant

ZnO films were deposited by metal-organic chemical vapor deposition on (0001) sapphire substrates at various partial pressure ratios of oxygen and zinc precursors (R_VI/II). The annealing and the R_VI/II ratio effects on the vibrational and optical properties of ZnO films have been investigated by Micro-Raman scattering and low temperature photoluminescence (PL) spectroscopy. As confirmed by characterizations used in this study, the quality of the ZnO films was improved by thermal annealing at 900 °C in oxygen ambient. Raman spectra of the as-deposited films show a broad band (BB) centered at about 518 cm⁻¹ whose intensity increases when the R_VI/II ratio decreases. After annealing, the intensity ratio of the BB to the E₂ high (E₂^H) peak decreases rapidly with increasing the annealing time (t_an). The vibrational properties of the annealed films grown at R_VI/II = 1 need only 1 h to be improved in contrast to those of films grown in Zn-rich condition, which need 4 h. From the E₂^H mode frequency, the residual stress in both the as-grown and the annealed films has been estimated. Micro-Raman measurements show that as-grown films are under a compressive stress which vanishes upon annealing and is not strongly dependent on t_an for t_an up to 1 h. PL spectra show that sharp donor bound exciton and A-free exciton emissions are observed for the as-deposited films grown at R_VI/II ≥ 0.5 and are enhanced after annealing for 1 h. However, in ZnO films grown in Zn-rich condition these emissions are absent and a t_an = 4 h is needed to annihilate non-radiative recombination centers and improve their luminescent efficiency.     

Effects of growth variables on the properties of single crystalline ZnO thin film grown by inductively coupled plasma metal organic chemical vapor deposition

Single crystalline undoped and Ga-doped n-type zinc oxide (ZnO) films were grown on sapphire (Al₂O₃) substrates by inductively coupled plasma (ICP) metal organic chemical vapor deposition. Effects of growth variables on the structural, optical, and electrical properties of ZnO films have been studied in detail. Single crystal films with flat and smooth surfaces were reproducibly obtained, with application of sample bias and O₂ ICP. The best film properties were obtained at the growth condition of 650 °C, 400 W ICP power, − 94 V bias voltage, O/Zn (VI/II) ratio of 75. Single crystalline Ga doped n-ZnO films were also obtained, with free carrier concentration of about 1.5 × 10¹⁹/cm³ at 1 at.% Ga concentration.     

Influence of ZnO/graphene nanolaminate periodicity on their structural and mechanical properties

Structural, electronic and mechanical properties of ZnO/Graphene (ZnO/G) nanolaminates fabricated by low temperature atomic layer deposition (ALD) and chemical vapor deposition (CVD) were investigated. We performed scanning and transmission electron microscopy (SEM/TEM), X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-Ray photoelectron spectroscopy (XPS) and nanoindentation to characterize the ZnO/G nanolaminates. The main structural and mechanical parameters of ZnO/G nanolaminates were calculated. The obtained results were analyzed and interpreted taking into account mechanical interaction and charge effects occurring at the G-ZnO interface. The influence of graphene sublayers number on the mechanical behavior of the ZnO/G nanolaminates was studied. By reducing the bilayer thickness, the mechanical parameters of the films can be tuned (Young’s modulus 100–200 GPa, hardness 3–9 GPa). The softer response of the multilayers as compared to the single layers of ZnO and graphene was attributed to the structural changes in the ZnO layer and the interfaces. This study shows the mechanical behavior of ZnO/G nanolaminates and their influence on the development of novel electro-optical devices based on these structures.     

不同衬底上氧化锌纳米结构的水热法制备研究

采用水热方法,以氯化锌和氨水为反应溶液,在铜和硅等不同基底上制备出不同特征的ZnO纳米棒和纳米管阵列.借助SEM和xRD等手段对其结构和形貌进行了分析研究.在常温下该样品表现出很好的光致发光性能.实验表明,在水热法中ZnO纳米材料的形貌、取向、排列等特征与衬底的选择有直接的关系.通过分析ZnO纳米管的形成过程,提出了一种新的由ZnO纳米棒在低温下溶解制得ZnO纳米管的生长机理.