Carbon nanotubes produced by tunneling of cobalt nanoparticles in carbon fibers

Carbon nanotubes (CNTs) have been produced by the tunneling of cobalt nanoparticles in carbon fibers that are derived from electrospun polyacrylonitrile (PAN) fibers. During annealing, the PAN fibers transform to a composite of cobalt nanodroplets and carbon fibers. Driven by the high chemical potential of wrinkled graphene platelets and amorphous carbon with respect to graphite, the cobalt nanodroplets are to tunnel in the carbon fibers. When cobalt nanodroplets have an elongated shape, carbon atoms dissolved in the droplets precipitate preferentially and completely at their lateral sides, producing perfect CNTs that form bulk structures. © 2012 Springer-Verlag Berlin Heidelberg.

A nanoliter volume nuclear magnetic resonance (NMR) system using tunneling magneto-resistive (TMR) sensors to recognize biomolecules

The need to incorporate advanced engineering tools in biology, biochemistry and medicine is in great demand. Many of the existing instruments and tools are usually expensive and require special facilities.^ With the advent of nanotechnology in the past decade, new approaches to develop devices and tools have been generated by academia and industry. ^ One such technology, NMR spectroscopy, has been used by biochemists for more than 2 decades to study the molecular structure of chemical compounds. However, NMR spectrometers are very expensive and require special laboratory rooms for their proper operation. High magnetic fields with strengths in the order of several Tesla make these instruments unaffordable to most research groups.^ This doctoral research proposes a new technology to develop NMR spectrometers that can operate at field strengths of less than 0.5 Tesla using an inexpensive permanent magnet and spin dependent nanoscale magnetic devices. This portable NMR system is intended to analyze samples as small as a few nanoliters.^ The main problem to resolve when downscaling the variables is to obtain an NMR signal with high Signal-To-Noise-Ratio (SNR). A special Tunneling Magneto-Resistive (TMR) sensor design was developed to achieve this goal. The minimum specifications for each component of the proposed NMR system were established. A complete NMR system was designed based on these minimum requirements. The goat was always to find cost effective realistic components. The novel design of the NMR system uses technologies such as Direct Digital Synthesis (DDS), Digital Signal Processing (DSP) and a special Backpropagation Neural Network that finds the best match of the NMR spectrum. The system was designed, calculated and simulated with excellent results.^ In addition, a general method to design TMR Sensors was developed. The technique was automated and a computer program was written to help the designer perform this task interactively.^

Components and circuits for tunneling diode based high frequency sources

Terahertz (THz) technology has been generating a lot of interest because of the potential applications for systems working in this frequency range. However, to fully achieve this potential, effective and efficient ways of generating controlled signals in the terahertz range are required. Devices that exhibit negative differential resistance (NDR) in a region of their current-voltage (I-V ) characteristics have been used in circuits for the generation of radio frequency signals. Of all of these NDR devices, resonant tunneling diode (RTD) oscillators, with their ability to oscillate in the THz range are considered as one of the most promising solid-state sources for terahertz signal generation at room temperature. There are however limitations and challenges with these devices, from inherent low output power usually in the range of micro-watts (uW) for RTD oscillators when milli-watts (mW) are desired. At device level, parasitic oscillations caused by the biasing line inductance when the device is biased in the NDR region prevent accurate device characterisation, which in turn prevents device modelling for computer simulations. This thesis describes work on I-V characterisation of tunnel diode (TD) and RTD (fabricated by Dr. Jue Wang) devices, and the radio frequency (RF) characterisation and small signal modelling of RTDs. The thesis also describes the design and measurement of hybrid TD oscillators for higher output power and the design and measurement of a planar Yagi antenna (fabricated by Khalid Alharbi) for THz applications. To enable oscillation free current-voltage characterisation of tunnel diodes, a commonly employed method is the use of a suitable resistor connected across the device to make the total differential resistance in the NDR region positive. However, this approach is not without problems as the value of the resistor has to satisfy certain conditions or else bias oscillations would still be present in the NDR region of the measured I-V characteristics. This method is difficult to use for RTDs which are fabricated on wafer due to the discrepancies in designed and actual resistance values of fabricated resistors using thin film technology. In this work, using pulsed DC rather than static DC measurements during device characterisation were shown to give accurate characteristics in the NDR region without the need for a stabilisation resistor. This approach allows for direct oscillation free characterisation for devices. Experimental results show that the I-V characterisation of tunnel diodes and RTD devices free of bias oscillations in the NDR region can be made. In this work, a new power-combining topology to address the limitations of low output power of TD and RTD oscillators is presented. The design employs the use of two oscillators biased separately, but with the combined output power from both collected at a single load. Compared to previous approaches, this method keeps the frequency of oscillation of the combined oscillators the same as for one of the oscillators. Experimental results with a hybrid circuit using two tunnel diode oscillators compared with a single oscillator design with similar values shows that the coupled oscillators produce double the output RF power of the single oscillator. This topology can be scaled for higher (up to terahertz) frequencies in the future by using RTD oscillators. Finally, a broadband Yagi antenna suitable for wireless communication at terahertz frequencies is presented in this thesis. The return loss of the antenna showed that the bandwidth is larger than the measured range (140-220 GHz). A new method was used to characterise the radiation pattern of the antenna in the E-plane. This was carried out on-wafer and the measured radiation pattern showed good agreement with the simulated pattern. In summary, this work makes important contributions to the accurate characterisation and modelling of TDs and RTDs, circuit-based techniques for power combining of high frequency TD or RTD oscillators, and to antennas suitable for on chip integration with high frequency oscillators.

Regioregular poly(3-hexyl-thiophene) helical self-organization on carbon nanotubes

Mixtures of Regioregular Poly(3-hexyl-thiophene) (rrP3HT) and multi wall carbon nanotubes have been investigated by Scanning Tunneling Microscopy in Ultra High Vacuum. Carbon nanotubes covered by rrP3HT have been imaged and analyzed, providing a clear evidence that this polymer self assembles on the nanotube surface following geometrical constraints and adapting its equilibrium chain-to-chain distance. Largely spaced covered nanotubes have been analyzed to investigate the role played by nanotube chirality in the polymer wrapping, evidencing strong rrP3HT interactions along well defined directions.

Manipulating double-decker molecules at the liquid-solid interface

We have used a scanning tunneling microscope to manipulate heteroleptic phthalocyaninato, naphthalocyaninato, porphyrinato double-decker molecules at the liquid/solid interface between 1-phenyloctane solvent and graphite. We employed nano-grafting of phthalocyanines with eight octyl chains to place these molecules into a matrix of heteroleptic double-decker molecules; the overlayer structure is epitaxial on graphite. We have also used nano-grafting to place double-decker molecules in matrices of single-layer phthalocyanines with octyl chains. Rectangular scans with a scanning tunneling microscope at low bias voltage resulted in the removal of the adsorbed doubledecker molecular layer and substituted the double-decker molecules with bilayer-stacked phthalocyanines from phenyloctane solution. Single heteroleptic double-decker molecules with lutetium sandwiched between naphthalocyanine and octaethylporphyrin were decomposed with voltage pulses from the probe tip; the top octaethylporphyrin ligand was removed and the bottom naphthalocyanine ligand remained on the surface. A domain of decomposed molecules was formed within the double-decker molecular domain, and the boundary of the decomposed molecular domain self-cured to become rectangular. We demonstrated a molecular “sliding block puzzle” with cascades of double-decker molecules on the graphite surface.

Microscopic and spectroscopic investigation of poly(3-hexylthiophene) interaction with carbon nanotubes

The inclusion of carbon nanotubes in polymer matrix has been proposed to enhance the polymer’s physical and electrical properties. In this study, microscopic and spectroscopic techniques are used to investigate the interaction between poly(3-hexylthiophene) (P3HT) and nanotubes and the reciprocal modification of physical properties. The presence of P3HT-covered nanotubes dispersed in the polymer matrix has been observed by atomic force microscopy and transmission electron microscopy. Then, the modification of P3HT optical properties due to nanotube inclusion has been evidenced with spectroscopic techniques like absorption and Raman spectroscopy. The study is completed with detailed nanoscale analysis by scanning probe techniques. The ordered self assembly of polymer adhering on the nanotube is unveiled by showing an example of helical wrapping of P3HT. Scanning tunneling spectroscopy study provides information on the electronic structure of nanotube-polymer assembly, revealing the charge transfer from P3HT to the nanotube.

Towards a controlled growth of self-assembled nanostructures: shaping, ordering and localization in Ge/Si heteroepitaxy.

The strain-induced self-assembly of suitable semiconductor pairs is an attractive natural route to nanofabrication. To bring to fruition their full potential for actual applications, individual nanostructures need to be combined into ordered patterns in which the location of each single unit is coupled with others and the surrounding environment. Within the Ge/Si model system, we analyze a number of examples of bottom-up strategies in which the shape, positioning, and actual growth mode of epitaxial nanostructures are tailored by manipulating the intrinsic physical processes of heteroepitaxy. The possibility of controlling elastic interactions and, hence, the configuration of self-assembled quantum dots by modulating surface orientation with the miscut angle is discussed. We focus on the use of atomic steps and step bunching as natural templates for nanodot clustering. Then, we consider several different patterning techniques which allow one to harness the natural self-organization dynamics of the system, such as: scanning tunneling nanolithography, focused ion beam and nanoindentation patterning. By analyzing the evolution of the dot assembly by scanning probe microscopy, we follow the pathway which leads to lateral ordering, discussing the thermodynamic and kinetic effects involved in selective nucleation on patterned substrates.

Polymer self assembly on carbon nanotubes

This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV–Vis and Raman), we show how the polymer’s higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT p-p stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.

Driving Ge island ordering on nanostructured Si surfaces

Semiconductor epitaxial nanostructures have been recently proposed as the key building blocks of many innovative applications in materials science and technology. To bring their tremendous potential to fruition, a fine control of nanostructure size and placement is necessary. We present a detailed investigation of the self-ordering process in the prototype case of Ge/Si heteroepitaxy. Starting from a bottom-up strategy (step-bunching instabilities), our analysis moves to lithographic techniques (scanning tunneling lithography, nanomechanical stamping, focused ion beam patterning) with the aim of developing a hybrid approach in which the exogenous intervention is specifically designed to suit and harness the natural self-organization dynamics of the system.

Characterisation of multi wall carbon nanotube–polymer composites for strain sensing applications

Carbon nanotubes (CNTs) have excellent electrical, mechanical and electromechanical properties. When CNTs are incorporated into polymers, electrically conductive composites with high electrical conductivity at very low CNT content (often below 1% wt CNT) result. Due to the change in electrical properties under mechanical load, carbon nanotube/polymer composites have attracted significant research interest especially due to their potential for application in in-situ monitoring of stress distribution and active control of strain sensing in composite structures or as strain sensors. To sucessfully develop novel devices for such applications, some of the major challenges that need to be overcome include; in-depth understanding of structure-electrical conductivity relationships, response of the composites under changing environmental conditions and piezoresistivity of different types of carbon nanotube/polymer sensing devices. In this thesis, direct current (DC) and alternating current (AC) conductivity of CNT-epoxy composites was investigated. Details of microstructure obtained by scanning electron microscopy were used to link observed electrical properties with structure using equivalent circuit modeling. The role of polymer coatings on macro and micro level electrical conductivity was investigated using atomic force microscopy. Thermal analysis and Raman spectroscopy were used to evaluate the heat flow and deformation of carbon nanotubes embedded in the epoxy, respectively, and related to temperature induced resistivity changes. A comparative assessment of piezoresistivity was conducted using randomly mixed carbon nanotube/epoxy composites, and new concept epoxy- and polyurethane-coated carbon nanotube films. The results indicate that equivalent circuit modelling is a reliable technique for estimating values of the resistance and capacitive components in linear, low aspect ratio-epoxy composites. Using this approach, the dominant role of tunneling resistance in determining the electrical conductivity was confirmed, a result further verified using conductive-atomic force microscopy analysis. Randomly mixed CNT-epoxy composites were found to be highly sensitive to mechanical strain and temperature variation compared to polymer-coated CNT films. In the vicinity of the glass transition temperature, the CNT-epoxy composites exhibited pronounced resistivity peaks. Thermal and Raman spectroscopy analyses indicated that this phenomenon can be attributed to physical aging of the epoxy matrix phase and structural rearrangement of the conductive network induced by matrix expansion. The resistivity of polymercoated CNT composites was mainly dominated by the intrinsic resistivity of CNTs and the CNT junctions, and their linear, weakly temperature sensitive response can be described by a modified Luttinger liquid model. Piezoresistivity of the polymer coated sensors was dominated by break up of the conducting carbon nanotube network and the consequent degradation of nanotube-nanotube contacts while that of the randomly mixed CNT-epoxy composites was determined by tunnelling resistance between neighbouring CNTs. This thesis has demonstrated that it is possible to use microstructure information to develop equivalent circuit models that are capable of representing the electrical conductivity of CNT/epoxy composites accurately. New designs of carbon nanotube based sensing devices, utilising carbon nanotube films as the key functional element, can be used to overcome the high temperature sensitivity of randomly mixed CNT/polymer composites without compromising on desired high strain sensitivity. This concept can be extended to develop large area intelligent CNT based coatings and targeted weak-point specific strain sensors for use in structural health monitoring.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Gold nanoresistors with near-constant resistivity in the cryogenic-to-room temperature range

Using a multiple plasma deposition-annealing (MDA) technique, we have fabricated an Au nanoisland-based thin film nanoresistor with a very low temperature coefficient of electrical resistivity in a cryogenic-to-room temperature range of 10 to 300 K. The nanoislanded gold film was deposited on a SiO2/Si wafer (500 nm SiO2 thickness) between two 300 nm thick Au electrodes which were separated by 100 m. A sophisticated selection of the thickness of the nanoislanded gold film, the annealing temperature, as well as the number of deposition/annealing cycles resulted in the fabrication of a nanoresistor with a temperature coefficient of electrical resistivity of 2.1 × 10-3 K-1 and the resistivity deviation not exceeding 2% in a cryogenic-to-room temperature range. We have found that the constant resistivity regime of the nanoisland-based thin film nanoresistor corresponds to a minimized nanoisland activation energy (approximately 0.3 meV). This energy can be minimized by reducing the nearest neighbor distance and increasing the size of the Au nanoislands in the optimized nanoresistor structure. It is shown that the constant resistivity nanoresistor operates in the regime where the thermally activated electron tunneling is compensated by the negative temperature dependence of the metallic-type conductivity of nanoislands. Our results are relevant to the development of commercially viable methods of nanoresistor production for various nanoelectronics-based devices. The proposed MDA technique also provides the opportunity to fabricate large arrays of metallic nanoparticles with controllable size, shapes and inter-nanoparticle gaps.

Effect of Coulomb blockade, gold resistance, and thermal expansion on the electrical resistance of ultrathin gold films

Controlling the electrical resistance of granular thin films is of great importance for many applications, yet a full understanding of electron transport in such films remains a major challenge. We have studied experimentally and by model calculations the temperature dependence of the electrical resistance of ultrathin gold films at temperatures between 2 K and 300 K. Using sputter deposition, the film morphology was varied from a discontinuous film of weakly coupled meandering islands to a continuous film of strongly coupled coalesced islands. In the weak-coupling regime, we compare the regular island array model, the cotunneling model, and the conduction percolation model with our experimental data. We show that the tunnel barriers and the Coulomb blockade energies are important at low temperatures and that the thermal expansion of the substrate and the island resistance affect the resistance at high temperatures. At low temperatures our experimental data show evidence for a transition from electron cotunneling to sequential tunneling but the data can also be interpreted in terms of conduction percolation. The resistivity and temperature coefficient of resistance of the meandering gold islands are found to resemble those of gold nanowires. We derive a simple expression for the temperature at which the resistance changes from non-metal-like behavior into metal-like behavior. In the case of strong island coupling, the total resistance is solely determined by the Ohmic island resistance.

Band gap tunable N-type molecules for organic field effect transistors

A series of four novel n-type molecules has been synthesized. Unlike previous approaches, the end group of these molecules was fixed and the molecular core was varied. The resulting materials were thoroughly analyzed. Electronic properties were derived from photoemission spectroscopy, optical properties were derived with the help of optical spectroscopy, and the structure of thin films on Au(111) was derived by scanning tunneling microscopy (STM). In addition, prototypical organic field-effect transistors (OFETs) (forming n-channels in OFETs) have been fabricated and tested. The correlation between the device performance of the respective OFETs (i.e., electron mobility) and their electronic as well as structural properties was investigated. It turned out that a combination of beneficial electronic and structural properties provides the best results. These findings are important for the design of new materials for future device applications.