A thermodynamic basis for the electronic properties of molten semiconductors: the role of electronic entropy

The thermodynamic origin of a relation between features of the phase diagrams and the electronic properties of molten semiconductors is provided. Leveraging a quantitative connection between electronic properties and entropy, a criterion is derived to establish whether a system will retain its semiconducting properties in the molten phase. It is shown that electronic entropy is critical to the thermodynamics of molten semiconductor systems, driving key features of phase diagrams including, for example, miscibility gaps. Keywords: entropy; electronic entropy; thermopower; molten semiconductorUnited States. Air Force Office of Scientific Research (Grant FA9550-15-1-0046

Wide range optical studies on transparent SWNT films

We present transmission spectra from the far infrared through the ultraviolet region on freestanding SWNT films at temperatures between 40 and 300 K. Several interesting features are observed in the low-frequency part of the spectrum: the Drude-like frequency dependence of the metallic tubes as well as a (sample-dependent) peak in the conductivity around 0.01 eV. We also studied the accidental nitrate doping of the SWNT samples during purification by nitric acid. Asprepared purified samples exhibit increased metallic absorption and decreased interband transitions; these features disappear on heating in vacuum

Electronic and structural properties of alkali doped SWNT

Comprehensive experiments on structural and transport properties of alkali intercalated single walled carbon nanotubes (SWNT) are presented. The increasing electron density was measured as a shift of the Drude-edge in optical reflectivity in-situ with progressive doping. In saturation-doped samples the Drude-edge shifts into the visible (to 25,000 - 30,000 cm— 1 for potassium and rubidium doped samples) and the samples have a golden-brown color, similar to stage I graphite. X-ray diffraction reveals a crystalline rope structure with expanded lattice constant, similar to results of Duclaux et al. The change in the low temperature divergence of the resistivity after degassing at high temperature and high vacuum and after K-doping is studied in-situ

Chemical doping of individual semiconducting carbon-nanotube ropes

We report the effects of potassium doping on the conductance of individual semiconducting single-walled carbon nanotube ropes. We are able to control the level of doping by reversibly intercalating and de-intercalating potassium. Potassium doping changes the carriers in the ropes from holes to electrons. Typical values for the carrier density are found to be ∼100–1000 electrons/μm. The effective mobility for the electrons is μeff∼20–60 cm2 V-1 s-1, a value similar to that reported for the hole effective mobility in nanotubes [R. Martel et al., Appl. Phys. Lett. 73, 2447 (1998)]

Study of charge dynamics in transparent single-walled carbon nanotube films

We report the transmission over a wide frequency range (far infrared - visible) of pristine and hole-doped, free-standing carbon nanotube films at temperatures between 50 K and 300 K. Optical constants are estimated by Kramers-Kronig analysis of transmittance. We see evidence in the far infrared for a gap below 10 meV. Hole doping causes a shift of spectral weight from the first interband transition into the far infrared. Temperature dependence in both the doped and undoped samples is restricted to the far-infrared region.Comment: 6 pages, 4 figures, submitted to Phys. Rev. B v3: Fig. 2 replaced, changes in caption of Table II, minor changes in tex

High-Current Field Emission from an Atomic Quantum Wire

Linear chains of carbon atoms have been proposed as the electron emitting structures of open tip carbon nanotubes subject to an electric field. To better understand the implications of the results of Smalley and collaborators, the electromagnetic response of linear carbon chains to both static and dynamics fields have been studied, making use of ab-initio methods. It is found that the associated emission currents, plotted as a function of the bias potential, follow Fowler-Nordheim intensity-voltage curves typical of the field emission of metallic tips. Under standard bias conditions, linear carbon chains of one nanometer of length are expected to deliver currents of the order of one microampere. These systems behave, furthermore, as conducting needles in photoabsorption processes. Linear carbon chains are thus likely to constitute the ultimate atomic-scale realization of metallic wires.Comment: 10 pages, 4 figures, RevTe

Hydrogen adsorption and cohesive energy of single-walled carbon nanotubes

Hydrogen adsorption on crystalline ropes of carbon single-walled nanotubes (SWNT) was found to exceed 8 wt.%, which is the highest capacity of any carbon material. Hydrogen is first adsorbed on the outer surfaces of the crystalline ropes. At pressures higher than about 40 bar at 80 K, however, a phase transition occurs where there is a separation of the individual SWNTs, and hydrogen is physisorbed on their exposed surfaces. The pressure of this phase transition provides a tube-tube cohesive energy for much of the material of 5 meV/C atom. This small cohesive energy is affected strongly by the quality of crystalline order in the ropes

Modified Fowler-Nordheim Field-Emission Formulae from a Nonplanar-Emitter Model

Field emission formulae, current-voltage characteristics and energy distribution of emitted electrons, are derived analytically for a nonplanar (hyperboloidal) metallic emitter model. The traditional Fowler-Nordheim formulae, which are derived from a planar emitter model, are modified, and the assumption of the planar emitter in the F-N model is reconsidered. Our analytical calculation also reveals the backgrounds of the previous numerical discussion by He et al. on the effect of the geometry of emitter on field emission. The new formulae contain a parameter which characterizes the sharpness of the hyperboloidal emitter, and experimental data of field emissions from clean tungsten emitters and nanotip emitters are analyzed by making use of this feature.Comment: 9 pages, 8 figure

Low temperature fullerene encapsulation in single wall carbon nanotubes: synthesis of N@C60_{60}@SWCNT

High filling of single wall carbon nanotubes (SWCNT) with C$_{60}$ and C$_{70}$ fullerenes in solvent is reported at temperatures as low as 69 $^{o}$C. A 2 hour long refluxing in n-hexane of the mixture of the fullerene and SWCNT results in a high yield of C$_{60}$,C$_{70}$@SWCNT, fullerene peapod, material. The peapod filling is characterized by TEM, Raman and electron energy loss spectroscopy and X-ray scattering. We applied the method to synthesize the temperature sensitive (N@C$_{60}$:C$_{60}$)@SWCNT as proved by electron spin resonance spectroscopy. The solvent prepared peapod samples can be transformed to double walled nanotubes enabling a high yield and industrially scalable production of DWCNT