Understanding and engineering interfacial charge transfer of carbon nanotubes and graphene for energy and sensing applications

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2013.Cataloged from PDF version of thesis.Includes bibliographical references.Graphene is a one-atom thick planar monolayer of sp2 -bonded carbon atoms organized in a hexagonal crystal lattice. A single walled carbon nanotube (SWCNT) can be thought of as a graphene sheet rolled up into a seamless hollow cylinder with extremely high length-to-diameter ratio. Their large surface area, and exceptional optical, mechanical and electronic properties make these low-dimensional carbon materials ideal candidates for (opto-)electronic and sensing applications. In this thesis I studied the charge transfer processes that occur at their interface, and developed applications based on the discovered properties. When light is incident on a semiconducting SWCNT, it can excite an electron from the valence band to the conduction band, thereby creating a Coulombically bound electron-hole pair, also known as an exciton. Excitons can decay via radiative or non-radiative recombination or by colliding with other excitons. They can diffuse along the length of a SWCNT or hop from larger band gap SWCNTs to smaller band gap SWCNTs, a process known as exciton energy transfer (EET). We studied their behavior as a function of temperature in SWCNT fibers and showed that at room temperature the rate constant for EET is more than two orders of magnitude larger than that of each of the different recombination processes. This led us to construct a core-shell SWCNT fiber, which consists of a core of smaller band gap SWCNTs, surrounded by a shell of larger band gap SWCNTs, essentially forming what is known as a type I heterojunction. In agreement with a model that describes exciton behavior in the SWCNT fibers, we found that upon illumination all the energy (in the form of excitons) was quickly transferred from the shell to the core, faster than the excitons would otherwise recombine. The SWCNT fiber proved to be an efficient optical and energetic concentrator. We showed that SWCNTs and poly(3-hexylthiophene) (P3HT) form a type II heterojunction, which implies that excitons generated in the P3HT can easily dissociate into free charge carriers at the interface with the SWCNTs. Despite this, the efficiency of a P3HT/SWCNT bulk heterojunction (BHJ) photovoltaic is subpar. We developed a P3HT/SWCNT planar heterojunction (PHJ) and achieved efficiencies that were 30 times higher, which showed that the formation of bundled aggregates in BHJs was the cause: metallic SWCNTs can quench the excitons in an entire bundle. Another interesting feature of our SWCNT/P3HT PHJ is that a maximum efficiency was reached when -60 nm of P3HT was used, which is surprising since in a planar photovoltaic a maximum is expected for ~8.5 nm of P3HT, the value of the exciton diffusion length. A Kinetic Monte Carlo simulation revealed that bulk exciton dissociation was responsible for the lower efficiencies observed in devices with low P3HT thickness. Next we created and studied a junction between SWCNTs and a monolayer of graphene, an ideal one-dimensional/two-dimensional carbon interface. We used Raman spectroscopy to probe the degree of charge transfer at the interface and based on a shift in the G peak position of the graphene Raman signal at the junction deduced that a typical metallic (semiconducting) SWCNT dopes the graphene with 1.12 x 1013 cm-2 (0.325 x 101 cm-2) electrons upon contact, in agreement with the fact that the Fermi level of the SWCNTs is more shallow than that of the graphene. A molecular dynamics simulation ruled out that the observed Raman peak shifts are due to strain, although it did show that SWCNTs are being compressed radially by the graphene sheet, resulting in a widening of their Raman peaks. We studied charge transfer between diazonium molecules and graphene, to better inform transistor and sensor design. The reaction rate depends on the degree of overlap between the filled energy levels in graphene and the unoccupied ones in the diazonium molecule. We showed that with increasing degree of functionalization the charge transfer characteristics of a graphene field effect transistor (FET) alter in the following ways: the minimum conductivity decreases, the Dirac point upshifts, the conductivity plateau at high carrier density decreases and the electronhole conduction asymmetry increases. We developed a theoretical model of charge transport in graphene FETs that takes into account the effect of both short-range and long-range scatterers. Fitting it to the charge-transport data reveals quantitative information about the number of impurities in the substrate supporting the graphene, about the number of defects created as a result of the reaction, and about the degree of electron-hole conduction asymmetry. Graphene functionalization also affects the graphene Raman signal. After reaction, the D to G intensity ratio to increases, which is a sign of covalent modification of the graphene lattice. Additionally, the G peak and 2D peak positions increase while the 2D/G intensity ratio decreases, which are signs of hole-doping. Based on a Raman analysis, we were also able to show that the end group of the diazonium salt can affect both the degree of chemisorption (covalent modification) as well as the degree of physisorption (doping). Finally, we studied the effects of charge transfer between graphene and biological cells on the graphene Raman signal and designed a fundamentally new type of biosensor. Graphene can be thought of as a continuous array of information units (sensor units). The Raman signal collected in each unit can report on its local environment. In contrast to graphene FET biosensors, the graphene Raman biosensor offers subcellular spatial resolution. The graphene Raman signal was shown to display a strong dependence on pH. Metabolically active cells acidify their local environment; therefore, pH is a proxy for cellular metabolism. We placed both human embryonic kidney (HEK) cells that were genetically engineered to produce mouse antibodies and control HEK cells that were not genetically modified onto the graphene. Based on the change in the graphene Raman signal we deduced the former have a metabolic rate that is four times higher than that of the control cells. Increased cellular adhesion allows the cells to interact more closely with the graphene monolayer and intensifies the observed Raman effects.by Geraldine L.C. Paulus.Ph.D

A graphene-based physiometer array for the analysis of single biological cells

A significant advantage of a graphene biosensor is that it inherently represents a continuum of independent and aligned sensor-units. We demonstrate a nanoscale version of a micro-physiometer – a device that measures cellular metabolic activity from the local acidification rate. Graphene functions as a matrix of independent pH sensors enabling subcellular detection of proton excretion. Raman spectroscopy shows that aqueous protons p-dope graphene – in agreement with established doping trajectories, and that graphene displays two distinct pKa values (2.9 and 14.2), corresponding to dopants physi- and chemisorbing to graphene respectively. The graphene physiometer allows micron spatial resolution and can differentiate immunoglobulin (IgG)-producing human embryonic kidney (HEK) cells from non-IgG-producing control cells. Population-based analyses allow mapping of phenotypic diversity, variances in metabolic activity, and cellular adhesion. Finally we show this platform can be extended to the detection of other analytes, e.g. dopamine. This work motivates the application of graphene as a unique biosensor for (sub)cellular interrogation.National Cancer Institute (U.S.) (Cancer Center Support (Core) Grant P30-CA14051)U.S. Army Research LaboratoryUnited States. Army Research Office. Institute for Soldier Nanotechnologies (Contract W911NF-13-D-0001)National Institute for Biomedical Imaging and Bioengineering (U.S.) (Grant P41EB015871-27)Skolkovo Institute of Science and Technolog

Transcription factor TFEB cell-autonomously modulates susceptibility to intestinal epithelial cell injury in vivo

Understanding the transcription factors that modulate epithelial resistance to injury is necessary for understanding intestinal homeostasis and injury repair processes. Recently, transcription factor EB (TFEB) was implicated in expression of autophagy and host defense genes in nematodes and mammalian cells. However, the in vivo roles of TFEB in the mammalian intestinal epithelium were not known. Here, we used mice with a conditional deletion of Tfeb in the intestinal epithelium (Tfeb ΔIEC) to examine its importance in defense against injury. Unperturbed Tfeb ΔIEC mice exhibited grossly normal intestinal epithelia, except for a defect in Paneth cell granules. Tfeb ΔIEC mice exhibited lower levels of lipoprotein ApoA1 expression, which is downregulated in Crohn’s disease patients and causally linked to colitis susceptibility. Upon environmental epithelial injury using dextran sodium sulfate (DSS), Tfeb ΔIEC mice exhibited exaggerated colitis. Thus, our study reveals that TFEB is critical for resistance to intestinal epithelial cell injury, potentially mediated by APOA1

Evolution of Physical and Electronic Structures of Bilayer Graphene upon Chemical Functionalization

The chemical behavior of bilayer graphene under strong covalent and noncovalent functionalization is relatively unknown compared to monolayer graphene, which has been far more widely studied. Bilayer graphene is significantly less chemically reactive than monolayer graphene, making it more challenging to study its chemistry in detail. However, bilayer graphene is increasingly attractive for electronic applications rather than monolayer graphene because of its electric-field-controllable band gap, and there is a need for a greater understanding of its chemical functionalization. In this paper, we study the covalent and noncovalent functionalization of bilayer graphene using an electrochemical process with aryl diazonium salts in the high conversion regime (D/G ratio >1), and we use Raman spectroscopic mapping and conductive atomic force microscopy (cAFM) to study the resulting changes in the physical and electronic structures. Covalent functionalization at high chemical conversion induces distinct changes in the Raman spectrum of bilayer graphene including the broadening and shift in position of the split G peak. Also, the D peak becomes active with four components. We report for the first time that the broadening of the 2D₂₂ and 2D₂₁ components is a distinct indicator of covalent functionalization, whereas the decrease in intensity of the 2D₁₁ and 2D₁₂ peaks corresponds to doping. Conductive AFM imaging shows physisorbed species from noncovalent functionalization can be removed by mechanical and electrical influence from the AFM tip, and that changes in conductivity due to functionalization are inhomogeneous. These results allow one to distinguish covalent from noncovalent chemistry as a guide for further studies of the chemistry of bilayer graphene

ARTICLE Metallized DNA nanolithography for encoding and transferring spatial information for graphene patterning

The vision for graphene and other two-dimensional electronics is the direct production of nanoelectronic circuits and barrier materials from a single precursor sheet. DNA origami and single-stranded tiles are powerful methods to encode complex shapes within a DNA sequence, but their translation to patterning other nanomaterials has been limited. Here we develop a metallized DNA nanolithography that allows transfer of spatial information to pattern two-dimensional nanomaterials capable of plasma etching. Width, orientation and curvature can be programmed by specific sequence design and transferred, as we demonstrate for graphene. Spatial resolution is limited by distortion of the DNA template upon Au metallization and subsequent etching. The metallized DNA mask allows for plasmonic enhanced Raman spectroscopy of the underlying graphene, providing information on defects, doping and lattice symmetry. This DNA nanolithography enables wafer-scale patterning of two-dimensional electronic materials to create diverse circuit elements, including nanorings, three-and four-membered nanojunctions, and extended nanoribbons

Excess Thermopower and the Theory of Thermopower Waves

Self propagating exothermic chemical reactions can generate electrical pulses when guided along a conductive conduit such as a carbon nanotube. However, these thermopower waves are not described bran existing theory to explain the origin of power generation or why its magnitude exceeds the predictions of the Seebeck effect In this work, we present a quantitative theory that describes the electrical dynamics of thermopower waves, showing that they produce an excess thermopower additive to the Seebeck prediction. Using synchronized, high-speed thermal, voltage, and wave velocity measurements, we link the additional power to the chemical potential gradient created by chemical reaction (up to 100 mV for picramide and sodium azide on carbon nanotubes). This theory accounts for the waves' unipolar voltage, their ability to propagate on good thermal conductors, and their high power, which Is up to 120% larger than conventional thermopower from a fiber of all-semiconducting SWNTs. These results underscore the potential to exceed, conventional figures of merit for thermoelectricity and allow us to bound the maximum power and efficiency attainable for such systems

Disorder Imposed Limits of Mono- and Bilayer Graphene Electronic Modification Using Covalent Chemistry

A central question in graphene chemistry is to what extent chemical modification can control an electronically accessible band gap in monolayer and bilayer graphene (MLG and BLG). Density functional theory predicts gaps in covalently functionalized graphene as high as 2 eV, while this approach neglects the fact that lattice symmetry breaking occurs over only a prescribed radius of nanometer dimension, which we label the S-region. Therefore, high chemical conversion is central to observing this band gap in transport. We use an electrochemical approach involving phenyl-diazonium salts to systematically probe electronic modification in MLG and BLG with increasing functionalization for the first time, obtaining the highest conversion values to date. We find that both MLG and BLG retain their relatively high conductivity after functionalization even at high conversion, as mobility losses are offset by increases in carrier concentration. For MLG, we find that band gap opening as measured during transport is linearly increased with respect to the <i>I</i>_<i>D</i>/<i>I</i>_<i>G</i> ratio but remains below 0.1 meV in magnitude for SiO₂ supported graphene. The largest transport band gap obtained in a suspended, highly functionalized (<i>I</i>_<i>D</i>/<i>I</i>_<i>G</i> = 4.5) graphene is about 1 meV, lower than our theoretical predictions considering the quantum interference effect between two neighboring S-regions and attributed to its population with midgap states. On the other hand, heavily functionalized BLG (<i>I</i>_<i>D</i>/<i>I</i>_<i>G</i> = 1.8) still retains its signature dual-gated band gap opening due to electric-field symmetry breaking. We find a notable asymmetric deflection of the charge neutrality point (CNP) under positive bias which increases the apparent on/off current ratio by 50%, suggesting that synergy between symmetry breaking, disorder, and quantum interference may allow the observation of new transistor phenomena. These important observations set definitive limits on the extent to which chemical modification can control graphene electronically