Ordered arrays of nanocrystals : synthesis, properties and applications

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.Vita.Includes bibliographical references.Nanoscale materials, including nanocrystals and carbon nanotubes, exhibit an appealing array of physical properties, and provide an interesting prospect for research both from a fundamental as well as a technological perspective. The current emerging themes in nanoscale research are: controlled synthesis with well defined sizes and geometries; unraveling their fundamental physical properties; and assembly of these nanoscale building blocks into functional devices. Although several approaches for producing the nanoparticles have been reported in the past decade, a general, large scale method for controlled synthesis of well-defined nanoparticles in the 1-5 nm size regimes is yet to be found. A general method that enables both syntheses of nanoparticles and their assembly on substrates is critical towards furthering technological applications. The work described here involved developing a method that utilized principles of self assembly in conjunction with inorganic and organic synthetic chemistry for the controlled synthesis of ordered arrays of nanocrystals. A unique attribute of this technique is it combined themes one and three, aforementioned, into a single step. First, uniform arrays of various mono- and hetero-bimetallic nanoparticles with sizes in the range of 1-5 nm were synthesized on various substrates using PS-P4VP block copolymer (BCP) templates. These arrays of monodisperse nanoparticles were employed as catalysts for the diameter-controlled growth of SWNTs.(cont.) Comparisons on their catalytic activities provided valuable insight on the catalyst-assisted growth of SWNTs. Alternate ways to improve the catalytic yield of nanotubes employing bi-metallic nanoparticles as well as novel catalysts for nanotube growth are also being reported for the first time. Importantly, a combinatorial approach involving BCPs and gas phase reactions was designed that enabled us in addressing some of the long standing problems associated with the syntheses of semiconductor III-Nitride nanocrystals. Finally, versatility of this synthesis method was further demonstrated by syntheses of ternary nitrides as well as rare earth ions doped GaN. While the investigations on the latter aspects are still in there infancy, initial results show significant promise and pave an exciting prospect for future studies.by Sreekar Bhaviripudi.Ph.D

High quality graphene synthesized by atmospheric pressure CVD on copper foil

Graphene was synthesized at 1000°C by Atmospheric Pressure Chemical Vapor Deposition on copper foil from methane diluted in argon and hydrogen. The influence of the main synthesis parameters was studied on 2x2 cm2 foils in order to obtain continuous monolayer graphene without crystalline defect. The uniformity, crystal quality and number of layers of graphene were analyzed by Raman spectroscopy and Scanning Electronic Microscopy. First, an increase of the annealing pre-treatment duration induced an increase of the average size of copper grains, leading to larger graphene flakes of higher crystallinity presenting a lower number of layers. Similar evolutions of graphene characteristics were observed when decreasing the methane concentration to 20 ppm, whereas an increase of run duration led to a loss of graphene quality and to a higher number of graphene layers, confirming that graphene formation is not self-limiting on copper. An optimum hydrogen/methane ratio was found, quite different from other results of the literature, probably due to differences in the copper pre-treatment step. Finally, an optimized three steps process was developed to form monolayer continuous graphene of high quality, successfully transposed to 7x7 cm2 substrates after a reactor scale-up

Triggering the Continuous Growth of Graphene toward Millimeter Size Grain

In this report, we demonstrated a simple but efficient strategy to synthesize millimeter-sized graphene single crystal grains by regulating the supply of reactants in chemical vapor deposition process. Polystyrene was used as a carbon source. Pulse heating on the carbon source was utilized to minimize the nucleation density of graphene on copper foil, while the gradual increase in the temperature of carbon source and the flow rate of hydrogen is adapted to drive the continuous growth of graphene grain. As a result, the nucleation density of graphene grain can be controlled as lower as ~100 nuclei/cm2, and the dimension of single crystal grain could grow up to ~1.2 mm. Raman spectroscopy, transmission electron microscopy and electrical transport measurement show that the graphene grains obtained are in high quality. The strategy presented here provides very good controllability and enables the possibility for large graphene single crystals, which is of vital importance for practical applications.Comment: 15 pages, 10 figures. accepted Advanced Functional materials 201

The control of graphene double-layer formation in copper-catalyzed chemical vapor deposition

The growth of graphene during Cu-catalyzed chemical vapor deposition was studied using 12CH4 and 13CH4 precursor gasses. We suggest that the growth begins by the formation of a multilayer cluster. This seed increases its size but the growth speed of a particular layer depends on its proximity to the copper surface. The layer closest to the substrate grows fastest and thus further limits the growth rate of the upper layers. Nevertheless, the growth of the upper layers continues until the copper surface is completely blocked. It is shown that the upper layers can be removed by modification of the conditions of the growth by hydrogen etching.Comment: 17 pages, 4 figure

Graphene transistors are insensitive to pH changes in solution

We observe very small gate-voltage shifts in the transfer characteristic of as-prepared graphene field-effect transistors (GFETs) when the pH of the buffer is changed. This observation is in strong contrast to Si-based ion-sensitive FETs. The low gate-shift of a GFET can be further reduced if the graphene surface is covered with a hydrophobic fluorobenzene layer. If a thin Al-oxide layer is applied instead, the opposite happens. This suggests that clean graphene does not sense the chemical potential of protons. A GFET can therefore be used as a reference electrode in an aqueous electrolyte. Our finding sheds light on the large variety of pH-induced gate shifts that have been published for GFETs in the recent literature

Control and Characterization of Individual Grains and Grain Boundaries in Graphene Grown by Chemical Vapor Deposition

The strong interest in graphene has motivated the scalable production of high quality graphene and graphene devices. Since large-scale graphene films synthesized to date are typically polycrystalline, it is important to characterize and control grain boundaries, generally believed to degrade graphene quality. Here we study single-crystal graphene grains synthesized by ambient CVD on polycrystalline Cu, and show how individual boundaries between coalescing grains affect graphene's electronic properties. The graphene grains show no definite epitaxial relationship with the Cu substrate, and can cross Cu grain boundaries. The edges of these grains are found to be predominantly parallel to zigzag directions. We show that grain boundaries give a significant Raman "D" peak, impede electrical transport, and induce prominent weak localization indicative of intervalley scattering in graphene. Finally, we demonstrate an approach using pre-patterned growth seeds to control graphene nucleation, opening a route towards scalable fabrication of single-crystal graphene devices without grain boundaries.Comment: New version with additional data. Accepted by Nature Material

Homogeneous bilayer graphene film based flexible transparent conductor

Graphene is considered a promising candidate to replace conventional transparent conductors due to its low opacity, high carrier mobility and flexible structure. Multi-layer graphene or stacked single layer graphenes have been investigated in the past but both have their drawbacks. The uniformity of multi-layer graphene is still questionable, and single layer graphene stacks require many transfer processes to achieve sufficiently low sheet resistance. In this work, bilayer graphene film grown with low pressure chemical vapor deposition was used as a transparent conductor for the first time. The technique was demonstrated to be highly efficient in fabricating a conductive and uniform transparent conductor compared to multi-layer or single layer graphene. Four transfers of bilayer graphene yielded a transparent conducting film with a sheet resistance of 180 {\Omega}_{\square} at a transmittance of 83%. In addition, bilayer graphene films transferred onto plastic substrate showed remarkable robustness against bending, with sheet resistance change less than 15% at 2.14% strain, a 20-fold improvement over commercial indium oxide films.Comment: Published in Nanoscale, Nov. 2011 : http://www.rsc.org/nanoscal

High quality monolayer graphene synthesized by resistive heating cold wall chemical vapour deposition

Emerging flexible and wearable technologies such as healthcare electronics and energy-harvest devices could be transformed by the unique properties of graphene. The vision for a graphene-driven industrial revolution is motivating intensive research on the synthesis of (1) high quality and (2) low cost graphene. Hot-wall chemical vapour deposition (CVD) is one of the most competitive growth methods, but its long processing times are incompatible with production lines. Here we demonstrate the growth of high quality monolayer graphene using a technique that is 100 times faster than standard hot-wall CVD, resulting in 99% reduction in production costs. A thorough complementary study of Raman spectroscopy, atomic force microscopy, scanning electron microscopy and electrical magneto-transport measurements shows that our cold wall CVD-grown graphene is of comparable quality to that of natural graphene. Finally, we demonstrate the first transparent and flexible graphene capacitive touch-sensor that could enable the development of artificial skin for robots.Comment: Bointon, T. H., Barnes, M. D., Russo, S. and Craciun, M. F. (2015), High Quality Monolayer Graphene Synthesized by Resistive Heating Cold Wall Chemical Vapor Deposition. Adv. Mater.. doi:10.1002/adma.20150160

Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum

Large single-crystal graphene is highly desired and important for the applications of graphene in electronics, as grain boundaries between graphene grains markedly degrade its quality and properties. Here we report the growth of millimetre-sized hexagonal single-crystal graphene and graphene films joined from such grains on Pt by ambient-pressure chemical vapour deposition. We report a bubbling method to transfer these single graphene grains and graphene films to arbitrary substrate, which is nondestructive not only to graphene, but also to the Pt substrates. The Pt substrates can be repeatedly used for graphene growth. The graphene shows high crystal quality with the reported lowest wrinkle height of 0.8 nm and a carrier mobility of greater than 7,100 cm2 V−1 s−1 under ambient conditions. The repeatable growth of graphene with large single-crystal grains on Pt and its nondestructive transfer may enable various applications

Three-Dimensional Graphene Nano-Networks with High Quality and Mass Production Capability via Precursor-Assisted Chemical Vapor Deposition

We report a novel approach to synthesize chemical vapor deposition-grown three-dimensional graphene nano-networks (3D-GNs) that can be mass produced with large-area coverage. Annealing of a PVA/iron precursor under a hydrogen environment, infiltrated into 3D-assembled-colloidal silicas reduces iron ions and generates few-layer graphene by precipitation of carbon on the iron surface. The 3D-GN can be grown on any electronic device-compatible substrate, such as Al2O3, Si, GaN, or Quartz. The conductivity and surface area of a 3D-GN are 52 S/cm and 1,025 m(2)/g, respectively, which are much better than the previously reported values. Furthermore, electrochemical double-layer capacitors based on the 3D-GN have superior supercapacitor performance with a specific capacitance of 245 F/g and 96.5% retention after 6,000 cycles due to the outstanding conductivity and large surface area. The excellent performance of the 3D-GN as an electrode for supercapacitors suggests the great potential of interconnected graphene networks in nano-electronic devices and energy-related materials.open15