Browsing by Subject "Graphene"

The development of electronic textiles, which have many potential healthcare and consumer applications, is currently limited by a lack of energy storage that can be effectively incorporated into such devices while having sufficient energy density, power density, and durability to perform well. The overall goal of this work was to improve the energy density and potential for use in electronic textile applications of a nanostructured composite of few-walled carbon nanotubes, manganese oxide, and reduced graphene oxide. Two approaches towards improving the desired properties by controlling the macroscopic structure of the composite were pursued: one, to make fiber or wire-shaped electrodes via wet-spinning in aqueous chitosan solutions (10% acetic acid), and the other, to make composite films with controlled porous structures using nitrocellulose as a sacrificial filler material. Both approaches yielded the desired macroscopic structures. The composite fibers were non-conductive due to the insulating nature of manganese oxide and its positioning on the surface of the fibers. Composite fibers of few-walled carbon nanotubes and reduced graphene oxide made by the same method were found to have good volumetric capacity, rate capability, stability and flexibility. Nonintuitively, electrochemical performance of composite films declined with increasing porosity due to a decrease in conductivity, highlighting the importance of balancing the interplay between properties important to device performance when designing controlled structures of complex materials.

Energy storage systems are critically important for many areas in modern society including consumer electronics, transportation and renewable energy production. This dissertation summarizes our efforts on improving the performance metrics of energy storage and conversion devices through rational design and fabrication of hybrid nanomaterial systems.

This dissertation is divided into five sections. The first section (chapter 2) describes comparison of graphene and carbon nanotubes (CNTs) on improving the specific capacitance of MnO2. We show that CNTs provided better performance when used as ultrathin electrodes but they both show similar performance with rapid MnO2 specific capacitance decrease as electrodes become thicker. We further designed ternary composite electrodes consisting of CNTs, graphene and MnO2 to improve thick electrode performance (chapter 3). We demonstrate that these electrodes were flexible and mechanically strong, had high electrical conductivity and delivered much higher capacity than electrodes made without CNTs.

Chapter 4 describes assembly of flexible asymmetric supercapacitors using a graphene/MnO2/CNTs flexible film as the positive electrode and an activated carbon/CNTs flexible film as the negative electrode. The devices were assembled using roll-up approach and can operate safely with 2 V in aqueous electrolytes. The major advantage of these devices is that they can deliver much higher energy under high power conditions compared with those designed by previous studies, reaching a specific energy of 24 Wh/kg at a power density of 7.8 kW/kg.

Chapter 5 describes our approach to improve the energy and power densities of nickel hydroxides for supercapacitors. This was done by assembling CNTs with Co-Ni hydroxides/graphene nanohybrids as freestanding electrodes. The assembled electrodes have dramatically improved performance metrics under practically relevant mass loading densities (~6 mg/cm2), reaching a specific capacitance of 2360 F/g at 0.5 A/g and 2030 F/g even at 20 A/g (~86% retention).

Finally, we discuss our efforts on designing highly active electrocatalysts based on winged nanotubes for oxygen reduction reactions (ORR). The winged nanotubes were prepared through controlled oxidization and exfoliation of stacked-cup nanotubes. When doped with nitrogen, they exhibited strong activity toward catalyzing ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance owning to their unique carbon structure.

The primary goals of this research were to investigate the electrochemical behavior of carbon nanostructures of varying morphology, identify morphological characteristics that improve electrochemical capacitance for applications in energy storage and neural stimulation, and engineer and characterize a boron-­doped diamond (BDD) electrode based electrochemical system for disinfection of human liquid waste.

Carbon nanostructures; ranging from vertically aligned multiwalled carbon nanotubes (MWCNTs), graphenated carbon nanotubes (g-­CNTs) to carbon nanosheets (CNS); were synthesized using a MPECVD system. The nanostructures were characterized by using scanning electron microscopy (SEM) and Raman spectroscopy. In addition to employing commonly used electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), a new technique was developed to evaluate the energy and power density of individual electrodes. This facilitated comparison of a variety of electrode materials without having to first develop complex device packaging schemes. It was found that smaller pore size and higher density of carbon foliates on a three-dimensional scaffold of carbon nanotubes increased specific capacitance. A design of experiments (DOE) study was conducted to explore the parametric space of the MWCNT system. A range of carbon nanostructures of varying morphology were obtained. It was observed that the capacitance was dependent on defect density. Capacitance increased with defect density.

A BDD electrode was characterized for use in a module designed to disinfect human liquid waste as a part of a new advanced energy neutral, water and additive-free toilet designed for treating waste at the point of source. The electrode was utilized in a batch process system that generated mixed oxidants from ions present in simulated urine and inactivated E. Coli bacteria. Among the mixed oxidants, the concentration of chlorine species was measured and was found to correlate to the reduction in E. Coli concentration. Finally, a new operating mode was developed that involved pulsing the voltage applied to the BDD anode led to 66% saving in energy required for disinfection and yet successfully reduced E. Coli concentration to less than the disinfection threshold.

Graphene is a novel carbon material with great promise for a range of applications due to its electronic and mechanical properties. Its two-dimensional nature translates to a high sensitivity to surface chemical interactions thereby making it an ideal platform for sensors. Graphene's electronic properties are not degraded due to mechanical flexing or strain (Kim, K. S., et al. nature 07719, 2009) offering another advantage for flexible sensors integrated into numerous systems including fabrics, etc.

We have demonstrated a graphene NO2 sensor on a solid substrate (100nm SiO2/heavily doped silicon). Three different methods were used to synthesize graphene and the sensor fabrication process was optimized accordingly. Water is used as a controllable p-type dopant in graphene to study the relationship between doping and graphene's response to NO2. Experimental results show that interface water between graphene and the supporting SiO2 substrate induces higher p-doping in graphene, leading to a higher sensitivity to NO2, consistent with theoretical predications (Zhang, Y. et al., Nanotechnology 20(2009) 185504).

We have also demonstrated a flexible and stretchable graphene-based sensor. Few layer graphene, grown on a Ni substrate, is etched and transferred to a highly stretchable polymer substrate (VHB from 3M) with preloaded stress, followed by metal contact formation to construct a flexible, stretchable sensor. With up to 500% deformation caused by compressive stress, graphene still shows stable electrical response to NO2. Our results suggest that higher compressive stress results in smaller sheet resistance and higher sensitivity to NO2.

A possible molecular detection sensor utilizing Surface Enhanced Raman Spectrum (SERS) based on a graphene/gallium nanoparticles platform is also studied. By correlating the enhancement of the graphene Raman modes with metal coverage, we propose that the Ga transfers electrons to the graphene creating local regions of enhanced electron concentration modifying the Raman scattering in graphene.

We report on graphene-based Superconductor-Normal metal-Superconductor Joseph- son junctions with contacts made from lead. The high transition temperature of this superconductor allows us to observe the supercurrent branch at temperatures up to 􏰆 2 K. We are able to detect a small, but non-zero, resistance despite the Josephson junctions being in the superconducting state. We attribute this resistance to the phase diffusion regime, which has not been yet identified in graphene. By measuring the resistance as a function of temperature and gate voltage, we can further charac- terize the nature of electromagnetic environment and dissipation in our samples. In addition we modulate the critical current through grapehene by an external magnetic field; the resulting Fraunhofer interference pattern shows several periods of oscilla- tions. However, deviations from the perfect Fraunhofer pattern are observed, and their cause is explained by a simulation that takes into account the sample design.

Graphene, first isolated in 2004 and the subject of the 2010 Nobel Prize in physics, has generated a tremendous amount of research interest in recent years due to its incredible mechanical and electrical properties. However, difficulties in large-scale production and low as-prepared surface area have hindered commercial applications. In this dissertation, a new material is described incorporating the superior electrical properties of graphene edge planes into the high surface area framework of carbon nanotube forests using a scalable and reproducible technology.

The objectives of this research were to investigate the growth parameters and mechanisms of a graphene-carbon nanotube hybrid nanomaterial termed “graphenated carbon nanotubes” (g-CNTs), examine the applicability of g-CNT materials for applications in electrochemical capacitors (supercapacitors) and cold-cathode field emission sources, and determine materials characteristics responsible for the superior performance of g-CNTs in these applications. The growth kinetics of multi-walled carbon nanotubes (MWNTs), grown by plasma-enhanced chemical vapor deposition (PECVD), was studied in order to understand the fundamental mechanisms governing the PECVD reaction process. Activation energies and diffusivities were determined for key reaction steps and a growth model was developed in response to these findings. Differences in the reaction kinetics between CNTs grown on single-crystal silicon and polysilicon were studied to aid in the incorporation of CNTs into microelectromechanical systems (MEMS) devices. To understand processing-property relationships for g-CNT materials, a Design of Experiments (DOE) analysis was performed for the purpose of determining the importance of various input parameters on the growth of g-CNTs, finding that varying temperature alone allows the resultant material to transition from CNTs to g-CNTs and finally carbon nanosheets (CNSs): vertically oriented sheets of few-layered graphene. In addition, a phenomenological model was developed for g-CNTs. By studying variations of graphene-CNT hybrid nanomaterials by Raman spectroscopy, a linear trend was discovered between their mean crystallite size and electrochemical capacitance. Finally, a new method for the calculation of nanomaterial surface area, more accurate than the standard BET technique, was created based on atomic layer deposition (ALD) of titanium oxide (TiO2).

Nonlinear optical microscopy serves as a great tool for biomedical imaging due to its high resolution, deep penetration, inherent three dimensional optical sectioning capabilities and superior performance in scattering media. Conventional nonlinear optical microscopy techniques, e.g. two photon fluorescence and second harmonic generation, are based on detecting a small light signal emitted at a new wavelength that is well separated from the excitation light. However, there are also many other nonlinear processes, such as two-photon absorption and self-phase modulation, that do not generate light at new wavelengths and that have not been extensively explored for imaging. This dissertation extends the accessible mechanisms for contrast to the later nonlinear optical processes by combining femtosecond laser pulse shaping and homodyne detection. We developed a rapid pulse shaper with a relatively simple and compact instrument design that modifies the spectrum of individual laser pulses from an 80 MHz mode-locked laser. The pulse shaper enables simultaneous two-photon absorption and self-phase modulation imaging of various nanoparticles in-vitro with high sensitivity. We also applied this imaging technique to study the nonlinear optical response in graphene. Because our technology detects the nonlinear signature encoded within the laser pulse itself, we achieve intrinsic contrast of biological and non-biological samples in highly scattering media. These capabilities have significant implications in biomedical imaging and nanophotonics.

Multiterminal Josephson junctions have attracted attention, driven by the promise that they may host synthetic topological phase of matter and provide insight into Floquet states. Indeed, the added complexity of the additional contacts in multiterminal Josephson junctions greatly expands its parameter space, allowing for unexpected results. This work sheds light onto the out of equilibrium superconducting states that can exist within a ballistic multiterminal Josephson junction. The application of a microwave excitation produces unexpected fractional Shapiro steps, which are a consequence of the multiterminal circuit network. The application of a finite voltage reveals a robust cos 2φ supercurrent along the multiplet biasing condition nV1=-mV2. This supercurrent is found to be born from the RCSJ equations and has a stability condition analogous to Kapitza’s pendulum. Finally, the injection of hot carriers poisons supercurrent contributions from the Andreev spectrum, revealing a continuum mediated supercurrent.

Graphene – a single atomic layer of graphite – is one of the most studied quasi two-dimensional materials (2D). Its electronic properties are particularly interesting, for example allowing one to study the physics of 2D relativistic electrons. Recently, graphene samples were coupled to superconducting leads, thus forming S-N-S (superconducting-normal-superconducting), or “Josephson” junctions. It was found that superconducting current (“supercurrent”) could flow through the normal (i.e. non-superconducting) graphene regions. The mechanism of this supercurrent is not fully explored. In this work, we study the supercurrent transport in three different regimes dependent on the electronic properties of graphene: diffusive, ballistic and quantum Hall (QH). In a diffusive device, the mean free path (scattering length) ξ_S of an electron is shorter than the length between the SC contacts, L. In the ballistic limit, the scattering length ξ_S exceeds L. These two regimes are explored without external magnetic field. On the other hand, the QH regime is induced by application of a strong magnetic field perpendicular to the plane of the sample. When the cyclotron radius rC is smaller than the junction length L/2, electron trajectories form closed orbits in the bulk of graphene and skipping orbits at the edge. Below I describe our findings in these regimes in more details.

For the diffusive case, the crucial energy scale is the Thouless energy, ETH = ħD/L^2, where D is diffusive constant. We find that the product of the critical current (maximal current through the device) and its normal resistance, I_CR_N, follows a universal linear dependence of E_TH for more than three orders of magnitude. However, the I_CR_N product is found to be much smaller than the theoretically predicted value of ~10E_TH/e.

To explore the ballistic regime, we worked with graphene encapsulated in hexagonal-Boron Nitride (h-BN), which greatly improves the transport properties of graphene. Here, we study the ballistic Josephson junctions in the short and long junction limits, determined by comparing the length of the junction with the induced superconducting coherence length. For the long junction limit, the temperature dependence of supercurrent is controlled by the energy level spacing as extracted from the Fabry-Perot (FP) oscillations. On the other hand, in the short junction limit, the superconducting gap will be the characteristic energy. Furthermore, we also study the supercurrent distribution in the graphene Josephson junctions by measuring the interference pattern in a small magnetic field. A unique periodicity modification around the Dirac point (DP) is observed.

Lastly, we demonstrate the first observation of supercurrent in the QH regime. Since in high magnetic fields the electron trajectories develop into cyclotron orbits, the bulk of the graphene is gapped by the so-called Landau quantization, and the only transport channels are chiral edge states on the borders of graphene. We study the magnetic interference of the supercurrent and demonstrate that the supercurrent indeed flows along the edges of the graphene region. Using different junction geometries, we examine possible mechanisms for this supercurrent. Our results may pave the way to realizing Majorana fermion or parafermion states predicted to be formed in certain hybrid QH-SC devices.

To conclude, we have explored supercurrent transport in multiple different regimes in the graphene Josephson junctions.

This dissertation presents the experimental methods and results of investigations into the nature of thermal and electronic transport at low temperatures in graphene superconducting devices. By coupling graphene to superconductors, we study the nature of complex supercurrent flow in graphene Josephson junctions. Small variations in magnetic fields are used to obtain information about the supercurrent distribution in rectangular two-terminal junctions, and anomalous interference patterns are observed in graphene close to the Dirac point. Extending the number of terminals to a four-terminal device allowed us to study the interplay of various supercurrents in the shared graphene region. Each of the observed supercurrents are identified as specific paths between pairs of terminals and are tracked as a function of charge density in the graphene. Multiple superconducting graphene devices are further studied under high magnetic fields to elucidate the potential transport mechanisms of supercurrent carried by quantum Hall edge states. Finally, we use large-domain graphene to fabricate devices across large length scales in order to study the interdependent heat transfer between electrons and phonons and diffusive electronic processes. With the ability to measure electronic temperature through Universal Conductance Fluctuations we study the heat flow directly as a function of length. Non-uniform thermal gradients are observed and related to equations describing the total heat flux in the graphene device.

The existence of supercurrent in the quantum Hall regime with periodic magnetic interference patterns, first observed by Amet et al. in 2016, has created new opportunities to access topological superconductivity through quantum Hall edge states. However, a puzzle is found in the measured h/2e periodicity, as it violates the theoretical predicted h/e periodicity of the supercurrents carried by chiral quantum Hall edge states. Thus the observed supercurrents have not yet been robustly confirmed.

In this dissertation, we study the transport mechanisms of supercurrents in the quantum Hall regime in graphene Josephson junctions. First, a device with individually gated vacuum edges extended beyond the contacts is studied to determine whether the measured supercurrents are consistent with the theoretical prediction that both edges participate in transport. Next, a device with a third normal contact on one vacuum edge is used to study how supercurrents are influenced by an injected normal current. Finally, a device with a T-shaped asymmetric contact and a flat contact separated by a 90nm short channel is fabricated to examine the coupling of the chiral electron-hole hybrid modes. Despite that fact that theoretical explanation of the h/2e periodicity are still outstanding, these studies have extended our understanding of supercurrents in the quantum Hall regime. This may lay the foundation of realizing Majorana fermions and parafermions with symmetry-breaking edge states in quantum Hall/superconductor hybrid devices.