Analyzing the molecular weight distribution in supramolecular polymers.

J Am Chem Soc 131:48 (2009) 17696-17704

Authors:

Stephan A Schmid, Robert Abbel, Albertus PH Schenning, EW Meijer, Rint P Sijbesma, Laura M Herz

Abstract:

We have investigated the formation process of supramolecular linear polymer chains and its influence on the resulting chain length distribution function. For this purpose, we explored the migration of excitation energy between oligofluorene units coupled together through quadruple hydrogen-bonding groups to form linear chains that are terminated by oligophenylene vinylene end-caps acting as energy traps. The energy transfer dynamics from the main chain to the chain end was monitored experimentally using time-resolved PL spectroscopy and compared to an equivalent Monte Carlo simulation incorporating information on the structure of the chains, the transition transfer rates, and various weight distribution trial functions. We find that the assumption of a Flory distribution of chain lengths leads to excellent agreement between experimental and simulated data for a wide range of end-cap concentrations. On the other hand, both a Poisson function and a simplified assumption of a monodisperse distribution significantly underestimate the presence of long chains in the ensemble. Our results therefore show that supramolecular polymerization is a steplike process equivalent to polycondensation reactions in linear covalent polymers. These findings emphasize that equal reactivity of the supramolecular building blocks leads to a dynamic growth process for the supramolecular chain involving all chain components at all times.

Terahertz excitonic response of isolated single-walled carbon nanotubes

Journal of Physical Chemistry C 113:42 (2009) 18106-18109

Authors:

X Xu, K Chuang, RJ Nicholas, MB Johnston, LM Herz

Abstract:

We have investigated the ultrafast far-infrared transmission of isolated single-walled carbon nanotubes using optical-pump THz-probe spectroscopy. The THz dielectric response is dominated by excitons with an initial, rapid decay due to Auger recombination followed by a slow decay of isolated single excitons. Frequencydependent analysis of the photomduced dielectric function suggest an internal excitonic excitation at ∼11 meV with further low-frequency (∼0.6 and 1.4 THz) absorption features at high densities ascribed to exciton complexes. A featureless conductivity bleaching is attributed to an exciton-induced reduction in the mobility of free carriers caused by phase-space filling. © 2009 American Chemical Society.

Carrier lifetime and mobility enhancement in nearly defect-free core-shell nanowires measured using time-resolved terahertz spectroscopy.

Nano Lett 9:9 (2009) 3349-3353

Authors:

Patrick Parkinson, Hannah J Joyce, Qiang Gao, Hark Hoe Tan, Xin Zhang, Jin Zou, Chennupati Jagadish, Laura M Herz, Michael B Johnston

Abstract:

We have used transient terahertz photoconductivity measurements to assess the efficacy of two-temperature growth and core-shell encapsulation techniques on the electronic properties of GaAs nanowires. We demonstrate that two-temperature growth of the GaAs core leads to an almost doubling in charge-carrier mobility and a tripling of carrier lifetime. In addition, overcoating the GaAs core with a larger-bandgap material is shown to reduce the density of surface traps by 82%, thereby enhancing the charge conductivity.

Conductivity of Nanoporous InP Membranes Investigated Using Terahertz Spectroscopy

Institute of Electrical and Electronics Engineers (IEEE) (2008) 707-708

Authors:

SKE Merchant, J Lloyd-Hughes, P Parkinson, LM Herz, MB Johnston, L Sirbu, IM Tiginyanu

Conductivity of nanoporous InP membranes investigated using terahertz spectroscopy.

Nanotechnology 19:39 (2008) 395704

Authors:

SKE Merchant, J Lloyd-Hughes, L Sirbu, IM Tiginyanu, P Parkinson, LM Herz, MB Johnston

Abstract:

We have investigated the terahertz conductivity of extrinsic and photoexcited electrons in nanoporous indium phosphide (InP) at different pore densities and orientations. The form of electronic transport in the film was found to differ significantly from that for bulk InP. While photo-generated electrons showed Drude-like transport, the behaviour for extrinsic electrons deviated significantly from the Drude model. Time-resolved photoconductivity measurements found that carrier recombination was slow, with lifetimes exceeding 1 ns for all porosities and orientations. When considered together, these findings suggest that the surfaces created by the nanopores strongly alter the dynamics of both extrinsic and photoexcited electrons.