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M Meyyappan

Publications and source records attributed to M Meyyappan.

At least 19 recordsLinked to original sources

Monolayer to multilayer nanostructural growth transition in N-type oligothiophenes on Au(111) and implications for organic field-effect transistor performance.

The evolution in growth morphology and molecular orientation of n-type semiconducting alpha,omega-diperfluorohexyl-quaterthiophene (DFH-4T) on Au(111) is investigated by scanning tunneling microscopy and scanning tunneling spectroscopy as the film thickness is increased from one monolayer to multilayers. Monolayer-thick DFH-4T films are amorphous and morphologically featureless with a large pit density, whereas multilayer films exhibit drastically different terraced structures consisting of overlapping platelets. Large changes in DFH-4T molecular orientation are observed on transitioning from two to four monolayers. Parallel electrical characterization of top-versus-bottom contact configuration DFH-4T FETs with Au source/drain electrodes reveals greatly different mobilities (mu(TOP) = 1.1 +/- 0.2 10(-2) cm(2)V(-1)s(-1) versus mu(BOTTOM) = 2.3 +/- 0.5 10(-5) cm(2)V(-1)s(-1)) and contact resistances (R(C-TOP) = 4-12 MOmegacm vs R(C-BOTTOM) > 1 GOmegacm). This study provides important information on the organic semiconductor-source\drain electrode interfaces and explains why top-contact OFET devices typically have superior performance. By direct visualization, it demonstrates that the DFH-4T film growth transition from monolayer to multilayer on Au is accompanied by dramatic morphology and molecular orientation changes, starting from an amorphous, pitted, and disordered monolayer, to crystalline and smooth bi/tetralayers but with the molecules reoriented by 90 degrees . These chemisorption-derived inhomogenities at the contact-molecule interface and the large monolayer --> multilayer --> bulk microstructural changes are in accord with the large bottom-contact device resistance and poor OFET performance.

Electric Conductivity↗

Dispersion of single-walled carbon nanotubes in a non-polar polymer, poly(4-methyl-1-pentene).

Poly(4-methyl-1-pentene), PMP, a high melting polymer composed of hydrogen and carbon, has the potential to become an alternative to polyethylene (PE) as shielding material against Galactic Cosmic Radiation (GCR). PMP exhibits higher thermal stability than PE and is transparent in the UV/visible region of the electromagnetic spectrum. Single walled carbon nanotubes (SWNTs) were pretreated with a polar solvent, N, N-Dimethylformimide (DMF), and then dispersed in a halogenated hydrocarbon, cyclohexyl chloride, which also dissolved the non polar polymer, PMP. The composites were characterized via differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), microhardness measurements, and optical microscopy. DMA data revealed that the carbon nanotubes contributed to the enhancement of the high temperature alpha(c) relaxation which is thought to arise from motion around crystalline regions in the matrix. The storage modulus (60 Hz) increased from 2409 MPa in the neat PMP to 3716 MPa at -50 degrees C. The magnitude of the increase diminished near and above the glass transition region; the glassy matrix restricted motion of the crystalline regions. DSC data showed an increase in the percent crystallinity of the composite (75%) as compared to the neat polymer (68%). Low concentrations of nanotubes, when well dispersed, produced nanocomposites with varying degrees of transparency.

Calorimetry, Differential Scanning↗

Functionalization of carbon nanotubes via nitrogen glow discharge.

We have exposed single-wall carbon nanotubes (SWCNTs) to microwave-generated N2 plasma with the aim to functionalize the nanotubes. The results strongly depend on the distance between the discharge source and the sample, since nitrogen atoms generated can be lost due to recombination. No functionalization was observed when this distance was 7.0 cm. At intermediate distances (2.5 cm), the incorporation of nitrogen and oxygen onto the SWCNT was observed, while, at short distances (1 cm), products containing CN were also observed.

Journal Article↗

Complex dynamics of carbon nanotube probe tips.

Carbon nanotube (CNT) tips in tapping mode atomic force microscopy (AFM) enable very high-resolution imaging, measurements, and manipulation at the nanoscale. We present recent results based on experimental analysis that yield new insights into the dynamics of CNT probe tips in tapping mode AFM. Experimental measurements are presented of the frequency response and dynamic amplitude-distance data of a high-aspect-ratio multi-walled (MW) CNT tip. Higher harmonics of the microcantilever are measured in frequency ranges corresponding to attractive regime and the repulsive regime where the CNT buckles dynamically. Surface scanning is performed using a MWCNT tip on a SiO(2) grating to verify the imaging instabilities associated with MWCNT buckling when used with normal control schemes in the tapping mode. Lastly, the choice of optimal setpoints for tapping mode control using CNT tip are discussed using the experimental results.

Journal Article↗

Mechanisms of 1D crystal growth in reactive vapor transport: indium nitride nanowires.

Indium nitride (InN) nanowire synthesis using indium (In) vapor transport in a dissociated ammonia environment (reactive vapor transport) is studied in detail to understand the nucleation and growth mechanisms involved with the so-called "self-catalysis" schemes. The results show that the nucleation of InN crystal occurs first on the substrate. Later, In droplets are formed on top of the InN crystals because of selective wetting of In onto InN crystals. Further growth via liquid-phase epitaxy through In droplets leads the growth in one dimension (1D), resulting in the formation of InN nanowires. The details about the nucleation and growth aspects within these self-catalysis schemes are rationalized further by demonstrating the growth of heteroepitaxially oriented nanowire arrays on single-crystal substrates and "tree-like" morphologies on a variety of substrates. However, the direct nitridation of In droplets using dissociated ammonia results in the spontaneous nucleation and basal growth of nanowires directly from the In melt surface, which is quite different from the above-mentioned nucleation mechanism with the reactive vapor transport case. The InN nanowires exhibit a band gap of 0.8 eV, whereas the mixed phase of InN and In(2)O(3) nanowires exhibit a peak at approximately 1.9 eV in addition to that at 0.8 eV.

Crystallization↗

Silicon nanowire synthesis by a vapor-liquid-solid approach.

Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.

Crystallization↗

charge storage behavior of nanowire transistors functionalized with bis(terpyridine)-Fe(II) molecules: dependence on molecular structure.

We studied the influence of three bis(terpyridine)-Fe(II) molecules-(X-tpy)2FeCl2 (X = H (1), SAc (2), and 4-phenyl-SAc (3)-on charge storage of a nanowire transistor. The molecules were assembled on the surface of an indium oxide nanowire that forms the conduction channel of the transistor. We found that the charge storage characteristics of such a device strongly depends on the structure of the terpyridine ligand: both retention time (tau) and threshold voltage shift (DeltaVth) increased in the order of 1 < 2 < 3, with tau of 200 s, 12 h, and 287 h and DeltaVth at 4.8, 12, and 28 V, respectively. Furthermore, when we placed the devices with molecules 1 and 3 in a vacuum and recorded the I-Vg curves in a two-day period, we observed higher hysteresis stability for device with molecule 3. For example, DeltaVth was reduced from 4.8 to 1.7 V for the device with molecule 1, while there was no reduction in DeltaVth for the device with molecule 2. These results suggest that thiolate headgroup and/or longer ligand length raises the charge tunneling barrier and results in longer charge retention and wider, more stable memory window. This work demonstrates the potential of chemical synthesis toward tailored device characteristics.

Journal Article↗

Carbon nanotube scanning probe for imaging in aqueous environment.

Carbon nanotubes (CNTs) used as a probe for scanning probe microscopy has become one of the many potential usages of CNTs that is finding real applications in scientific research and industrial communities. It has been proposed that the unique mechanical buckling properties of the CNT would lessen the imaging force exerted on the sample and, thus, make CNT scanning probes ideal for imaging soft materials, including biological samples in liquid environments. The hydrophobic nature of the CNT graphitic sidewall is clearly chemically incompatible with the aqueous solution requirements in some biological imaging applications. In this paper, we present electron micrograph results demonstrating the instability of CNT scanning probes when submerged in aqueous solution. Moreover, we also introduce a novel approach to resolve this chemical incompatibility problem. By coating the CNT probe with ethylenediamine, thus rendering the CNT probe less hydrophobic, we demonstrate the liquid imaging capability of treated CNT probes. Experimental data for imaging in aqueous solutions are presented, which include an ultrathin Ir film and DNA molecules on a mica surface.

Ethylenediamines↗

Improvement of thermal contact resistance by carbon nanotubes and nanofibers.

Interfacial thermal resistance results of various nanotube and nanofiber coatings, prepared by chemical vapor deposition (CVD) methods, are reported at relatively low clamping pressures. The five types of samples examined include multi-walled and single-walled nanotubes growth by CVD, multi-walled nanotubes grown by plasma enhanced CVD (PECVD) and carbon nanofibers of differing aspect ratio grown by PECVD. Of the samples examined, only high aspect ratio nanofibers and thermally grown multi-walled nanotubes show an improvement in thermal contact resistance. The improvement is approximately a 60% lower thermal resistance than a bare Si-Cu interface and is comparable to that attained by commercially available thermal interface materials.

Crystallization↗

System optimization for the development of ultrasensitive electronic biosensors using carbon nanotube nanoelectrode arrays.

Vertically aligned multi-walled carbon nanotubes (MWCNTs) have been reported in fabricating nanoelectrode arrays. Further studies on optimizing this system for the development of ultrasensitive DNA sensors are reported here. The mechanical stability of the as-grown MWCNT array can be improved by polymer coating or SiO2 encapsulation. The latter method provides excellent electronic and ionic insulation to the sidewall of MWCNTs and the underlying metal layer, which is investigated with electrochemical impedance spectroscopy. The insulation ensures well-defined nanoelectrode behavior. A method is developed for selectively functionalizing biomolecules at the open end of MWCNTs while keeping the SiO2 surface passivated, using the unique graphitic chemistry. An ultrahigh sensitivity approaching the limit of fluorescence techniques is obtained with this system for DNA detection.

Base Sequence↗

Topography and transport properties of oligo(phenylene ethynylene) molecular wires studied by scanning tunneling microscopy.

Conjugated phenylene(ethynylene) molecular wires are of interest as potential candidates for molecular electronic devices. Scanning tunneling microscopic study of the topography and current-voltage (I-V) characteristics of self-assembled monolayers of two types of molecular wires are presented here. The study shows that the topography and I-Vs, for small scan voltages, of the two wires are quite similar and that the electronic and structural changes introduced by the substitution of an electronegative N atom in the central phenyl ring of these wires does not significantly alter the self-assembly or the transport properties.

Electrochemistry↗

Plasma-enhanced chemical vapor deposition of multiwalled carbon nanofibers.

Plasma-enhanced chemical vapor deposition is used to grow vertically aligned multiwalled carbon nanofibers (MWNFs). The graphite basal planes in these nanofibers are not parallel as in nanotubes; instead they exhibit a small angle resembling a stacked cone arrangement. A parametric study with varying process parameters such as growth temperature, feedstock composition, and substrate power has been conducted, and these parameters are found to influence the growth rate, diameter, and morphology. The well-aligned MWNFs are suitable for fabricating electrode systems in sensor and device development.

Carbon↗

Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics.

A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

Carbon Dioxide↗

Modeling of the HiPco process for carbon nanotube production. II. Reactor-scale analysis.

The high-pressure carbon monoxide (HiPco) process, developed at Rice University, has been reported to produce single-walled carbon nanotubes from gas-phase reactions of iron carbonyl in carbon monoxide at high pressures (10-100 atm). Computational modeling is used here to develop an understanding of the HiPco process. A detailed kinetic model of the HiPco process that includes of the precursor, decomposition metal cluster formation and growth, and carbon nanotube growth was developed in the previous article (Part I). Decomposition of precursor molecules is necessary to initiate metal cluster formation. The metal clusters serve as catalysts for carbon nanotube growth. The diameter of metal clusters and number of atoms in these clusters are some of the essential information for predicting carbon nanotube formation and growth, which is then modeled by the Boudouard reaction with metal catalysts. Based on the detailed model simulations, a reduced kinetic model was also developed in Part I for use in reactor-scale flowfield calculations. Here this reduced kinetic model is integrated with a two-dimensional axisymmetric reactor flow model to predict reactor performance. Carbon nanotube growth is examined with respect to several process variables (peripheral jet temperature, reactor pressure, and Fe(CO)5 concentration) with the use of the axisymmetric model, and the computed results are compared with existing experimental data. The model yields most of the qualitative trends observed in the experiments and helps to understanding the fundamental processes in HiPco carbon nanotube production.

Carbon Dioxide↗

Decreased expression and activity of the immediate-early growth response (Egr-1) gene product during cellular senescence.

Human diploid fibroblasts (HDFs) undergo a limited number of population doublings in culture before reaching the end of their proliferative life span, an event termed in vitro cellular senescence. Considerable evidence suggests that altered expression of key genes involved in the mitogenic response may be responsible for the inability of senescent cells to proliferate. Here we examined the expression and activity of the early growth response-1 (egr-1) gene, an "immediate-early" gene that is believed to link extracellular mitogenic signals to cell-cycle progression. We found that egr-1 was strongly downregulated in senescent HDFs at the level of mRNA, protein, and DNA binding activity. Decreased DNA binding activity of Egr-1 in vitro corresponded to decreased transcriptional activation in vivo. To further understand the mechanism of egr-1 downregulation, we examined the potential role of the serum response elements (SREs) present in the egr-1 promoter. Electrophoretic mobility shift studies using young and old cell nuclear extracts showed a marked decrease in serum response factor (SRF) binding activity to the SRE in old compared to young cells. Loss of SRF binding activity has been correlated with the loss of expression of another growth-related immediate-early gene (c-fos). These results suggest a common mechanism for the downregulation of c-fos, egr-1, and other SRE-dependent, mitogen-responsive genes during cellular senescence.

Cells, Cultured↗

Increased expression of cyclin D2 during multiple states of growth arrest in primary and established cells.

Cyclin D2 is a member of the family of D-type cyclins that is implicated in cell cycle regulation, differentiation, and oncogenic transformation. To better understand the role of this cyclin in the control of cell proliferation, cyclin D2 expression was monitored under various growth conditions in primary human and established murine fibroblasts. In different states of cellular growth arrest initiated by contact inhibition, serum starvation, or cellular senescence, marked increases (5- to 20-fold) were seen in the expression levels of cyclin D2 mRNA and protein. Indirect immunofluorescence studies showed that cyclin D2 protein localized to the nucleus in G0, suggesting a nuclear function for cyclin D2 in quiescent cells. Cyclin D2 was also found to be associated with the cyclin-dependent kinases CDK2 and CDK4 but not CDK6 during growth arrest. Cyclin D2-CDK2 complexes increased in amounts but were inactive as histone H1 kinases in quiescent cells. Transient transfection and needle microinjection of cyclin D2 expression constructs demonstrated that overexpression of cyclin D2 protein efficiently inhibited cell cycle progression and DNA synthesis. These data suggest that in addition to a role in promoting cell cycle progression through phosphorylation of retinoblastoma family proteins in some cell systems, cyclin D2 may contribute to the induction and/or maintenance of a nonproliferative state, possibly through sequestration of the CDK2 catalytic subunit.

3T3 Cells↗

Allosteric uncoupling after chronic benzodiazepine exposure of recombinant gamma-aminobutyric acid(A) receptors expressed in Sf9 cells: ligand efficacy and subtype selectivity.

By using the baculovirus expression system, we report decreases in allosteric coupling at individual gamma-aminobutyric acid (GABA)(A) receptor subtypes (alpha-1, beta-2 and gamma-2, alpha-2, beta-3 and gamma-2 and alpha-5, beta-3 and gamma-2) after chronic benzodiazepine exposure that replicate coupling changes measured in rat cortical membranes after in vivo benzodiazepine exposure. The appearance of uncoupling was time-dependent and the magnitude of uncoupling at expressed GABA(A) receptor subtypes after chronic exposure was dependent upon the efficacy of the ligand in a subtype-specific manner. In addition, the expression of uncoupling was not accompanied by changes in benzodiazepine receptor number or affinity at any expressed GABA(A) subtype examined. The specificity of the coupling change was further shown by the ability of a brief exposure to the benzodiazepine receptor antagonist, Ro15-1788, to reverse the uncoupling induced by chronic benzodiazepine exposure. These findings suggest that alterations at the GABA(A) receptor complex after chronic benzodiazepine exposure are mediated directly by agonist effects at the GABA(A) receptor complex and are not the product of the changes in the surrounding neuronal environment. Furthermore, the present study shows that drug efficacy, and not simply affinity, plays a critical role in determining the degree of uncoupling, and perhaps, in the development of tolerance and dependence.

Allosteric Regulation↗