Kofi W. Adu

Experimental probes of the molecular hydrogen–carbon nanotube interaction

Electrical transport (resistance R and thermoelectric power S), Raman scattering, and hydrogen adsorption are used to study the interaction of hydrogen molecules with ropes of single-walled carbon nanotubes. The data are consistent with H2 physisorption under the experimental conditions investigated (4 KoTo500 K; 0.1 atmoPo20 atm). The response of S; R to 1 atm hydrogen at 500 Kis consistent with the introduction of a new scattering channel for electrons/holes in the metallic tubes. Raman scattering from the Q-branch of hydrogen molecules adsorbed on the surface is found shifted only by 1–2 cm � 1 from their frequencies in the free molecule and indicates that two different adsorption sites can be detected. Finally, H2 wt% storage in heavily processed ropes of SWNTs are found to exceed 6% at B1 atm and T ¼ 77 Kand the isosteric heat of adsorption is found to be 120 meV. r 2002 Elsevier Science B.V. All rights reserved.

Morphological, structural, and chemical effects in response of novel carbide derived carbon sensor to NH3, N2O, and air.

The response of two carbide derived carbons (CDCs) films to NH(3), N(2)O, and room air is investigated by four probe resistance at room temperature and pressures up to 760 Torr. The two CDC films were synthesized at 600 (CDC-600) and 1000 degrees C (CDC-1000) to vary the carbon morphology from completely amorphous to more ordered, and determine the role of structure, surface area, and porosity on sensor response. Sensor response time followed kinetic diameter and indicated a more ordered carbon structure slowed response due to increased tortuosity caused by the formation of graphitic layers at the particle fringe. Steady state sensor response was greater for the less-ordered material, despite its decreased surface area, decreased micropore volume, and less favorable surface chemistry, suggesting carbon structure is a stronger predictor of sensor response than surface chemistry. The lack of correlation between adsorption of the probe gases and sensor response suggests chemical interaction (charge transfer) drive sensor response within the material; N(2)O response, in particular, did not follow simple adsorption behavior. Based on Raman and FTIR characterization, carbon morphology (disorder) appeared to be the determining factor in overall sensor response, likely due to increased charge transfer between gases and carbon defects of amorphous or disordered regions. The response of the amorphous CDC-600 film to NH(3) was 45% without prior oxidation, showing amorphous CDCs have promise as chemical sensors without additional pretreatment common to other carbon sensors.

Probing Phonons in Nonpolar Semiconducting Nanowires with Raman Spectroscopy

We present recent developments in Raman probe of confined optical and acoustic phonons in nonpolar semiconducting nanowires, with emphasis on Si and Ge. First, a review of the theoretical spatial correlation phenomenological model widely used to explain the downshift and asymmetric broadening to lower energies observed in the Raman profile is given. Second, we discuss the influence of local inhomogeneous laser heating and its interplay with phonon confinement on Si and Ge Raman line shape. Finally, acoustic phonon confinement, its effect on thermal conductivity, and factors that lead to phonon damping are discussed in light of their broad implications on nanodevice fabrication.

External Electric Field Effect on Electrons Transport in Carbon Nanotubes

We consider a simple model of carbon nanotubes (CNTs) subject to external electric field E(t). Using a tight-binding approximation for the description of energy bands of CNTs, together with the standard Boltzmann transport equation and constant relaxation time, we predict the effect of self-induced transparency and absolute negative conductivity. The predicted effects may be useful in diagnostics of carbon nanotubes as well as in the amplification and efficiency conversion of electromagnetic signals.

PHONONS IN SILICON NANOWIRES

Cubic silicon in bulk form has changed the modern landscape of electronics and electro-optics. The physical and chemical properties of Si are perhaps the best understood of any crystalline solid. It is therefore a crucial crystalline material to research and understand the possibilities for new devices at the nanoscale where quantum confinement phenomena drive the formation of new electronic and phonon states. In this chapter, we focus on phonon properties expected for “confined” Si in the form of nanowires. We review calculations of the phonon dispersion in small diameter nanowires as well as experiments that seek to probe the change in the phonon dispersion and the associated physical properties. Discussion is presented on the observation and interpretation of data on inelastic light scattering from nanowire phonons (Raman and Brillouin Spectroscopy), thermal conductivity and specific heat.

Flexible robust binder-free carbon nanotube membranes for solid state and microcapacitor application

We present a liquid phase post synthesis self-assemble protocol that transforms trillions of carbon nanotubes (CNTs) in powder form into densely packed flexible, robust and binder-free macroscopic membranes with a hierarchical pore structure. We employ charge transfer engineering to spontaneously disperse the CNTs in a liquid medium. The processing protocol has limited or no impact on the intrinsic properties of the CNTs. As the thickness of the CNT membrane is increased, we observed a gradual transition from high flexibility to buckling and brittleness in the flexural properties of the membranes. The binder-free CNT membranes have bulk mass density greater than that of water (1.0 g cm-3). We correlate the mass of the CNTs in the membrane to the thickness of the membrane and obtained a bulk mass density of ∼1.11 g cm-3 ± 0.03 g cm-3. We demonstrate the use of the CNT membranes as electrode in a pristine and oxidized single/stacked solid-state capacitor as well as pristine interdigitated microcapacitor that show time constant of ∼32 ms with no degradation in performance even after 10 000 cycles. The capacitors show very good temperature dependence over a wide range of temperatures with good cycling performance up to 90 °C. The specific capacitance of the pseudocapacitive CNT electrode at room temperature was 72 F g-1 and increased to 100 F g-1 at 70 °C. The leakage current of bipolar stacked solid state capacitor was ∼100 nA cm-2 at 2.5 V when held for 72 h.

Amplification of terahertz radiation in carbon nanotubes

We investigate theoretically the feasibility of amplification of terahertz radiation in aligned achiral carbon nanotubes, a zigzag (12,0) and an armchair (10,10) in comparison with a superlattice using a combination of a constant direct current (dc) and a high-frequency alternate current (ac) electric fields. The electric current density expression is derived using the semiclassical Boltzmann transport equation with a constant relaxation time. The electric field is applied along the nanotube axis. Analysis of the current density versus electric field characteristics reveals a negative differential conductivity behavior at high frequency, as well as photon assisted peaks. The photon assisted peaks are about an order of magnitude higher in the carbon nanotubes compared to the superlattice. These strong phenomena in carbon nanotubes can be used to obtain domainless amplification of terahertz radiation at room temperature.

Magnetic quenching of photonic activity in Fe3O4-elastomer composite

Abstract. We report a quenching phenomenon within the visible region of the electromagnetic spectrum in the photonic response of a passive Fe3O4-silicone elastomer composite film due to magnetically aligned Fe3O4 nanoparticles. We performed systematic studies of the polarization dependence, the effect of particle size, and an in- and out-of-plane particle alignment on the optical response of the Fe3O4-silicone elastomer composites using a UV/vis/NIR spectrometer. We observed systematic redshifts in the response of the out-of-plane composite films with increasing particle alignment and weight that are attributed to dipole-induced effects. There were no observable shifts in the spectra of the in-plane films, suggesting the orientation of the magnetic dipole and the induced electric dipole play a crucial role in the optical response. A dramatic suppression to near quenching of the photonic response occurred in films containing moderate concentrations of the aligned nanoparticles. This is attributed to the interplay between the intra- and the interparticle dipoles. This occurred even when low magnetic fields were used during the curing process, suggesting that particle alignment and particle size limitation are critical in the manipulation of the photonic properties. A dipole approximation model is used to explain the quenching phenomenon. An active system of such a composite has a potential application in magneto-optic switches.

DEVELOPMENT OF DOPED NANOPOROUS CARBONS FOR HYDROGEN STORAGE

Hydrogen storage materials based on the hydrogen spillover mechanism onto metal-doped nanoporous carbons are studied, in an effort to develop materials that store appreciable hydrogen at ambient temperatures and moderate pressures. We demonstrate that oxidation of the carbon surface can significantly increase the hydrogen uptake of these materials, primarily at low pressure. Trace water present in the system plays a role in the development of active sites, and may further be used as a strategy to increase uptake. Increased surface density of oxygen groups led to a significant enhancement of hydrogen spillover at pressures less than 100 milibar. At 300K, the hydrogen uptake was up to 1.1 wt. % at 100 mbar and increased to 1.4 wt. % at 20 bar. However, only 0.4 wt% of this was desorbable via a pressure reduction at room temperature, and the high lowpressure hydrogen uptake was found only when trace water was present during pretreatment. Although far from DOE hydrogen storage targets, storage at ambient temperature has significant practical advantages oner cryogenic physical adsorbents. The role of trace water in surface modification has significant implications for reproducibility in the field. High-pressure in situ characterization of ideal carbon surfaces in hydrogen suggests re-hybridization is not likely under conditions of practical interest. Advanced characterization is used to probe carbon-hydrogen-metal interactions in a number of systems and new carbon materials have been developed.

Silicon Nanowires: Doping Dependent N- And P- Channel FET Behavior

The electrical transport properties of field effect transistor (FET) devices made of silicon nanowires (SiNWs) synthesized by pulsed laser vaporization (PLV) were studied. From as-grown PLV-SiNW FET, we found pchannel FET behavior with low conductance. To improve conductance, spin on glass (SOG) and vapor doping were used to dope phosphorus and indium into SiNW, respectively. From doping after synthesis, we could successfully make both nand p-channel FET devices. Comments Copyright Materials Research Society. Reprinted from MRS Proceedings Volume 832. 2004 Fall Meeting Symposium F Group-IV Semiconductor Nanostructures Publisher URL: http://www.mrs.org/s_mrs/sec_subscribe.asp?CID=2689&DID=114852&action=detail This conference paper is available at ScholarlyCommons: http://repository.upenn.edu/mse_papers/80 SILICON NANOWIRES: DOPING DEPENDENT NAND PCHANNEL FET BEHAVIOR Kumhyo Byon and John E. Fischer Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104, U.S.A. Kofi W. Adu and Peter. C. Eklund Department of Physics, Pennsylvania State University, University Park, PA 16803, U.S.A.