Chemical modification of graphene via hyperthermal molecular reaction.

Chemical functionalization of graphene is achieved by hyperthermal reaction with azopyridine molecular ions. The one-step, room temperature process takes place in high vacuum (10(-7) mbar) using an electrospray ion beam deposition (ES-IBD) setup. For ion surface collisions exceeding a threshold kinetic energy of 165 eV, molecular cation beams of 4,4'-azobis(pyridine) covalently attach to chemical vapor deposited (CVD) graphene. A covalent functionalization degree of 3% of the carbon atoms of graphene is reached after 3-5 h of ion exposure of 2 × 10(14) azopyridinium/cm(2) of which 50% bind covalently. This facile approach for the controlled modification of graphene extends the scope of candidate species that would not otherwise react via existing conventional methods.

Enrichment of large-diameter semiconducting SWCNTs by polyfluorene extraction for high network density thin film transistors.

A systematic study on the use of 9,9-dialkylfluorene homopolymers (PFs) for large-diameter semiconducting (sc-) single-walled carbon nanotube (SWCNT) enrichment is the focus of this report. The enrichment is based on a simple three-step extraction process: (1) dispersion of as-produced SWCNTs in a PF solution; (2) centrifugation at a low speed to separate the enriched sc-tubes; (3) filtration to collect the enriched sc-SWCNTs and remove excess polymer. The effect of the extraction conditions on the purity and yield including molecular weight and alkyl side-chain length of the polymers, SWCNT concentration, and polymer/SWCNT ratio have been examined. It was observed that PFs with alkyl chain lengths of C10, C12, C14, and C18, all have an excellent capability to enrich laser-ablation sc-SWCNTs when their molecular weight is larger than ∼10 000 Da. More detailed studies were therefore carried out with the C12 polymer, poly(9,9-di-n-dodecylfluorene), PFDD. It was found that a high polymer/SWCNT ratio leads to an enhanced yield but a reduced sc-purity. A ratio of 0.5-1.0 gives an excellent sc-purity and a yield of 5-10% in a single extraction as assessed by UV-vis-NIR absorption spectra. The yield can also be promoted by multiple extractions while maintaining high sc-purity. Mechanistic experiments involving time-lapse dispersion studies reveal that m-SWCNTs have a lower propensity to be dispersed, yielding a sc-SWCNT enriched material in the supernatant. Dispersion stability studies with partially enriched sc-SWCNT material further reveal that m-SWCNTs : PFDD complexes will re-aggregate faster than sc-SWCNTs : PFDD complexes, providing further sc-SWCNT enrichment. This result confirms that the enrichment was due to the much tighter bundles in raw materials and the more rapid bundling in dispersion of the m-SWCNTs. The sc-purity is also confirmed by Raman spectroscopy and photoluminescence excitation (PLE) mapping. The latter shows that the enriched sc-SWCNT sample has a narrow chirality and diameter distribution dominated by the (10,9) species with d = 1.29 nm. The enriched sc-SWCNTs allow a simple drop-casting method to form a dense nanotube network on SiO2/Si substrates, leading to thin film transistors (TFTs) with an average mobility of 27 cm(2) V(-1) s(-1) and an average on/off current ratio of 1.8 × 10(6) when considering all 25 devices having 25 µm channel length prepared on a single chip. The results presented herein demonstrate how an easily scalable technique provides large-diameter sc-SWCNTs with high purity, further enabling the best TFT performance reported to date for conjugated polymer enriched sc-SWCNTs.

Highly sensitive electrical detection of TCNE on chemically passivated silicon-on-insulator.

Adsorption of tetracyanoethylene (TCNE) onto hydrogen terminated, n-type silicon-on-insulator is shown to cause significant depletion of majority carriers. Employing an ambient pseudo-MOSFET, ppm levels of TCNE vapour rapidly decrease the n-channel saturation current by at least two orders of magnitude. Covalent passivation with a decyl monolayer improves the reversibility of the response while only slightly decreasing the sensitivity.

Molecular modulation of conductivity on H-terminated silicon-on-insulator substrates.

The adsorption of a range of molecular species (water, pyridine, and ammonia) is found to reversibly modulate the conductivity of hydrogen-terminated silicon-on-insulator (H-SOI) substrates. Simultaneous sheet-resistance and Hall-effect measurements on moderately doped (10(15) cm(-3)) n- and p-type H-SOI samples mounted in a vacuum system are used to monitor the effect of gas exposure in the Torr range on the electrical-transport properties of these substrates. Reversible physisorption of "hole-trapping" species, such as pyridine (C(5)H(5)N) and ammonia (NH(3)) produces highly conductive minority-carrier channels (inversion) on p-type substrates, mimicking the action of a metallic gate in a field-effect transistor. The adsorption of these same molecules on n-type SOI induces strong electron-accumulation layers. Minority/majority channels are also formed upon controlled exposure to water vapor. These observations can be explained by a classical band-bending model, which considers the adsorbates as the source of a uniform surface charge ranging from +10(11) to +10(12)q cm(-2). These results demonstrate the utility of DC transport measurements of SOI platforms for studies of molecular adsorption and charge-transfer effects at semiconductor surfaces.