No abstract

A cryogenic variable-temperature ultra-high vacuum scanning tunneling microscope is used for measuring the electrical properties of isolated cyclopentene molecules adsorbed to the degenerately p-type Si(100)-2؋1 surface at a temperature of 80 K. Currentvoltage curves taken under these conditions show negative differential resistance at positive sample bias, in agreement with previous observations at room temperature. Because of the enhanced stability of the scanning tunneling microscope at cryogenic temperatures, repeated measurements can be routinely taken over the same molecule. Taking advantage of this improved stability, we show that current-voltage curves on isolated cyclopentene molecules are reproducible and possess negligible hysteresis for a given tip-molecule distance. On the other hand, subsequent measurements with variable tip position show that the negative differential resistance voltage increases with increasing tipmolecule distance. By using a one-dimensional capacitive equivalent circuit and a resonant tunneling model, this behavior can be quantitatively explained, thus providing insight into the electrostatic potential distribution across a semiconductor-moleculevacuum-metal tunnel junction. This model also provides a quantitative estimate for the alignment of the highest occupied molecular orbital of cyclopentene with respect to the Fermi level of the silicon substrate, thus suggesting that this experimental approach can be used for performing chemical spectroscopy at the single-molecule level on semiconductor surfaces. Overall, these results serve as the basis for a series of design rules that can be applied to silicon-based molecular electronic devices.cyclopentene ͉ resonant tunneling ͉ molecular electronics ͉ capacitance ͉ spectroscopy S ince the seminal paper of Aviram and Ratner (1), the field of molecular electronics has undergone rapid growth. Many research efforts are probing the unique charge-transport properties of individual molecules with hopes of revolutionizing electronics and computation. A common experimental approach in this field is to vary the structure of the organic molecule that is placed between two metal electrodes (2-14). However, recent reports suggest that the contacts themselves play a pivotal role in the observed charge-transport behavior of several of these devices (15). This development suggests that, in addition to different molecular systems, alternative contact materials may lead to unique electronic functionality. Because of its compatibility with organic chemistry, its semiconductor band structure, and its ubiquity in commercially available microelectronics, silicon is a promising alternative substrate for molecular electronics.Concurrent with the recent developments in molecular electronics, the ultra-high vacuum (UHV) scanning tunneling microscope (STM) has advanced well beyond its original purpose of probing the structure and properties of materials at atomic length scales (16). Atom manipulation (17-21), nanolithography (22-25), chemical modification (2...

Arc discharge single-walled carbon nanotubes (SWCNTs) possess superlative optical and electronic properties that are of high interest for technologically important applications including fiber optic communications, biomedical imaging, and field-effect transistors. However, as-grown arc discharge SWCNTs possess a mixture of metallic and semiconducting species in addition to a wide diameter distribution (1.2 to 1.7 nm) that limit their performance in devices. While previous postsynthetic sorting efforts have achieved separation by electronic type and diameter refinement for metallic arc discharge SWCNTs, tight diameter distributions of semiconducting arc discharge SWCNTs have not yet been realized. Herein, we present two advances in density gradient ultracentrifugation that enable the isolation of high purity (>99%) semiconducting arc discharge SWCNTs with narrow diameter distributions centered at ∼1.6 and ∼1.4 nm. The resulting diameter-refined populations of semiconducting arc discharge SWCNTs possess monodisperse characteristics that are well-suited for high-performance optical and electronic technologies.

Electron stimulated desorption of cyclopentene from the Si(100)-(2 x 1) surface is studied experimentally with cryogenic UHV STM and theoretically with transport, electronic structure, and dynamical calculations. Unexpectedly for a saturated hydrocarbon on silicon, desorption is observed at bias magnitudes as low as 2.5 V, albeit the desorption yields are a factor of 500 to 1000 lower than previously reported for unsaturated molecules on silicon. The low threshold voltage for desorption is attributed to hybridization of the molecule with the silicon surface, which results in low-lying ionic resonances within 2-3 eV of the Fermi level. These resonances are long-lived, spatially localized, and displaced in equilibrium with respect to the neutral state. This study highlights the importance of nuclear dynamics in silicon-based molecular electronics and suggests new guidelines for the control of such dynamics.

The design and performance of a variable temperature ultrahigh vacuum (UHV) scanning tunneling microscope (STM) is presented. This STM operates from 8.2 to 300 K in a UHV environment with a base pressure of less than 6×10−11 Torr. Cooling is achieved from 300 to 80 K within 3.5 h and from 80 to 8.2 K within 4.5 h. The base temperature of 8.2 K is maintained at a liquid helium consumption rate of 0.9 l/h. This design allows for direct optical access to the tip-sample interface and direct line-of-sight dosing while the sample is mounted in the STM. The STM tip may be coarse translated laterally in two dimensions through a 6-mm-diam area at all temperatures. With the feedback loop off, the drift in the tip-sample spacing is approximately 0.008 Å/min at 8.2 K. Atomic resolution feedback controlled lithography is performed on hydrogen passivated Si(100) and differential tunneling conductance maps are gathered for isolated cyclopentene molecules on unpassivated Si(100), thus demonstrating that this system is well suited for studying single molecules on silicon surfaces from 8.2 to 300 K.