Ultrafast charge generation in a semiconducting polymer studied with THz emission spectroscopy

Euan Hendry, Mattijs Koeberg, Juleon M. Schins, L. D. A. Siebbeles, and Mischa Bonn, Physical Review B, Vol. 70, article 033202 (2004). "Copyright © 2004 by the American Physical Society."We study the ultrafast charge generation in a semiconducting polymer (MEH-PPV) by measuring the radiated THz field after photoexciting the biased polymer with a femtosecond visible pulse. The subpicosecond temporal characteristics of the emitted wave reflects the ultrafast photoconductivity dynamics and sets an upper limit for charge generation of 200 fs following photoexcitation, and reveals the dispersive nature of charge transport in MEH-PPV. A comparison of the fields radiated from MEH-PPV and the well-characterized model semiconductor system (GaAs) allows for an accurate estimate of the quantum efficiency for charge generation in the polymer, found to be less than 1% . Both observations are consistent with ultrafast charge generation in semiconducting polymers through hot exciton dissociation

Temperature dependence of the charge carrier mobility in gated quasi-one-dimensional systems

The many-body Monte Carlo method is used to evaluate the frequency dependent conductivity and the average mobility of a system of hopping charges, electronic or ionic on a one-dimensional chain or channel of finite length. Two cases are considered: the chain is connected to electrodes and in the other case the chain is confined giving zero dc conduction. The concentration of charge is varied using a gate electrode. At low temperatures and with the presence of an injection barrier, the mobility is an oscillatory function of density. This is due to the phenomenon of charge density pinning. Mobility changes occur due to the co-operative pinning and unpinning of the distribution. At high temperatures, we find that the electron-electron interaction reduces the mobility monotonically with density, but perhaps not as much as one might intuitively expect because the path summation favour the in-phase contributions to the mobility, i.e. the sequential paths in which the carriers have to wait for the one in front to exit and so on. The carrier interactions produce a frequency dependent mobility which is of the same order as the change in the dc mobility with density, i.e. it is a comparably weak effect. However, when combined with an injection barrier or intrinsic disorder, the interactions reduce the free volume and amplify disorder by making it non-local and this can explain the too early onset of frequency dependence in the conductivity of some high mobility quasi-one-dimensional organic materials.Comment: 9 pages, 8 figures, to be published in Physical Review

Interchain effects in the ultrafast photophysics of a semiconducting polymer: THz time-domain spectroscopy of thin films and isolated chains in solution

Euan Hendry, Mattijs Koeberg, Juleon M. Schins, H. K. Nienhuys, V. Sundström, L. D. A. Siebbeles, and Mischa Bonn, Physical Review B, Vol. 71, article 125201 (2005). "Copyright © 2005 by the American Physical Society."We compare the generation and decay dynamics of charges and excitons in a model polymer semiconductor (MEH-PPV) in solution and drop-cast thin films, by recording the sub-ps transient complex conductivity using THz time-domain spectroscopy. The results show that the quantum efficiency of charge generation is two orders of magnitude smaller in solution (~10–5) than in the solid film (~10–3). The proximity of neighboring chains in the films apparently facilitates (hot) exciton dissociation, presumably by allowing the electron and hole to separate on different polymer strands. For both samples, photoexcitation leads to the predominant formation of bound charge pairs (excitons) that can be detected through their polarizability. Surprisingly, the polarizability per absorbed photon is a factor of 3 larger in solution than in the film, suggesting that interchain interactions in the film do not result in a substantial delocalization of the exciton wave function

Tuning of the excited state properties of phenylenevinylene oligomers:A time-dependent density functional theory study

This paper discusses a time-dependent density functional theory study of the effect of molecular structure on the excited state polarizability of conjugated molecules. A short phenylenevinylene oligomer containing three phenyl rings (PV2, distyryl benzene) is taken as a model system. Introduction of methyl substituents is shown to have only a small influence on the increase in polarizability upon excitation (the excess polarizability, Delta(alpha) over bar). Methoxy groups have a much larger effect but in this case Delta(alpha) over bar depends strongly on the dihedral angle between the side chain and the backbone of the molecule. If the central phenyl ring of PV2 has a meta-configuration rather than para, both the optical absorption spectrum and the excess polarizability change considerably. (C) 2003 American Institute of Physics

Efficiency of Exciton and Charge Carrier Photogeneration in a Semiconducting Polymer

Euan Hendry, Juleon M. Schins, L. P. Candeias, L. D. A. Siebbeles, and Mischa Bonn, Physical Review Letters, Vol. 92, article 196601 (2004). "Copyright © 2004 by the American Physical Society."We determine the efficiencies for the formation of excitons and charge carriers following ultrafast photoexcitation of a semiconducting polymer (MEH-PPV). The simultaneous, quantitative determination of exciton and charge photoyields is achieved through subpicosecond studies of both the real and the imaginary components of the complex conductivity over a wide frequency range. Predominantly excitons, with near-unity quantum efficiency, are generated on excitation, while only a very small fraction (<10-2) of free charges are initially excited, consistent with rapid (∼100  fs) hot exciton dissociation. These initial charges are very short lived, decaying on subpicosecond time scales

Efficient photogeneration of charge carriers in silicon nanowires with a radial doping gradient

From electrodeless time-resolved microwave conductivity measurements, the efficiency of charge carrier generation, their mobility, and decay kinetics on photo-excitation were studied in arrays of Si nanowires grown by the vapor-liquid-solid mechanism. A large enhancement in the magnitude of the photoconductance and charge carrier lifetime are found depending on the incorporation of impurities during the growth. They are explained by the internal electric field that builds up, due to a higher doped sidewalls, as revealed by detailed analysis of the nanowire morphology and chemical composition

Change in Tetracene Polymorphism Facilitates Triplet Transfer in Singlet Fission-Sensitized Silicon Solar Cells

Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si) then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here we show that a change in the polymorphism of tetracene deposited on Si due to air exposure, facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photocurrent. The decay of tetracene delayed photoluminescence was used to determine a triplet transfer time of 215 ns and a maximum yield of triplet transfer into Si of ~50 %. Our study suggests that control over the morphology of tetracene during deposition will be of great importance to boost the triplet transfer yield further

Spatially, Temporally and Polarization-Resolved Photoluminescence Exploration of Excitons in Crystalline Phthalocyanine Thin Films

The lack of long range order in organic semiconductor thin films prevents the unveiling of the complete nature of excitons in optical experiments, because the diffraction limited beam diameters in the bandgap region far exceed typical crystalline grain sizes. Here we present spatially-, temporally- and polarization-resolved dual photoluminescence/linear dichroism microscopy experiments that investigate exciton states within a single crystalline grain in solution-processed phthalocyanine thin films. These experiments reveal the existence of a delocalized singlet exciton, polarized along the high mobility axis in this quasi-1D electronic system. The strong delocalized {\pi} orbitals overlap controlled by the molecular stacking along the high mobility axis is responsible for breaking the radiative recombination selection rules. Using our linear dichroism scanning microscopy setup we further established a rotation of molecules (i.e. a structural phase transition) that occurs above 100 K prevents the observation of this exciton at room temperature.Comment: submitted to Journal of Chem Phys letter