Theory of photoinduced charge transfer in weakly coupled donor-acceptor conjugated polymers: application to an MEH-PPV:CN-PPV pair

In a pair of coupled donor-acceptor conjugated polymer chains, it is possible for an exciton photoexcited on either polymer to decay into a hole in the donor polymer's valence band and an electron in the conduction band of the acceptor polymer. We calculate the corresponding exciton decay rate and its dependence on inter-polymer distance. For a pair of derivatives of poly(phenylene vinylene), PPV, specifically poly[2-methoxy, 5-(2$^\prime$-ethyl-hexyloxy)-1, 4 PPV], MEH-PPV, and poly(2,5-hexyloxy $p$-phenylene cyanovinylene), CN-PPV, at a separation of 6 \AA the characteristic decay time is 2.2 ps, whereas at 4 \AA it is $\sim 50$ fs.Comment: 9 pages, RevTeX, 4 PS files, to be published in a special issue of Chem. Phy

Negative capacitance in organic semiconductor devices: bipolar injection and charge recombination mechanism

We report negative capacitance at low frequencies in organic semiconductor based diodes and show that it appears only under bipolar injection conditions. We account quantitatively for this phenomenon by the recombination current due to electron-hole annihilation. Simple addition of the recombination current to the well established model of space charge limited current in the presence of traps, yields excellent fits to the experimentally measured admittance data. The dependence of the extracted characteristic recombination time on the bias voltage is indicative of a recombination process which is mediated by localized traps.Comment: 3 pages, 3 figures, accepted for publication in Applied Physics Letter

Random laser action in self-organized para-sexiphenyl nanofibers grown by hot-wall epitaxy

We report on the observation of amplified spontaneous emission and random lasing in self-organized crystalline para-sexiphenyl nanofibers. Using subpicosecond excitation, a lasing threshold is observed on the 0-1 emission band near 425 nm at excitation fluences as low as 0.5 muJ/cm(2) (6x10(16) cm(-3) equivalent density), near the onset of density-dependent recombination processes. The dependence of the nonlinear emission spectrum on both the pump intensity and position of the excitation area are attributed to the interplay between random lasing and amplified spontaneous emission occurring along the nanofibers

Molecular crystal approach for pi-conjugated polymers: from PPP Hamiltonian to Holstein model for polaron states

Starting from the $\pi$-electron Pariser-Parr-Pople (PPP) Hamiltonian which includes both strong electron-phonon and electron-electron interactions, we propose some strongly correlated wave functions of increasing quality for the ground state of conjugated polymers. These wavefunctions are built by combining different finite sets of local configurations extended at most over two nearest-neighbour monomers. With this picture, the doped case with one additional particle is expressed in terms of quasi-particle. Thus, the polaron formation problem goes back to the study of a Holstein like model.Comment: 27 pages, 6 eps figs, Revtex; enlarged version. Submitted to Journal of Physics: Condensed Matte

Effect of interchain separation on the photoinduced absorption spectra of polycarbazolyldiacetylenes

The photoinduced absorption spectra of a novel polycarbazolyldiacetylene with long aliphatic chains on the carbazolyl side groups are measured and compared with those of the unsubstituted polyDCHD. The two polymers in the blue form exhibit very similar electronic absorption spectra and Raman frequencies. This fact indicates that the conjugation length of the polydiacetylene backbone is not too affected by the long substituents. In contrast, the near steady-state photoinduced absorption spectra show that different photogeneration mechanisms are involved in the two polymers. This result can be ascribed to the role played by the interchain distance in the dynamics of the relaxation processes in polydiacetylenes

Electroluminescence in polymer-fullerene photovoltaic cells

We report electroluminescence (EL) in photovoltaic (PV) cells based on semiconducting polymer-fullerene composites. By applying a forward bias to the PV cells, the devices exhibited a clear EL action with a peak around 1.5 eV. We ascribe this peak to an "electric field-assisted exciplex" formed between the electrons in the fullerenes and the holes in the polymers, thereby resulting in radiative recombination in the composites. This finding is totally unexpected because of a strong photoluminescence quenching in the same materials. Since the same devices also showed typical photovoltaic effects under illumination, our results demonstrate a dual functionality in one device; polymer photovoltaic cells and polymer light-emitting diodes.open464

Transient optical studies of charge recombination dynamics in a polymer/fullerene composite at room temperature

The recombination kinetics of photogenerated charge carriers in a composite of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1-4-phenylene vinylene], (MDMO–PPV) and the functionalised fullerene 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 are investigated at room temperature by transient absorption spectroscopy. The decay dynamics of positively charged MDMO–PPV polarons were found to be either monophasic or biphasic, depending upon the laser excitation density employed. The slower, power law, decay phase (100 ns–10 ms) is attributed to recombination dynamics of localized polarons, while the fast decay component (<20 ns) is attributed to recombination of relatively mobile polarons observed when the density of localized states is exceeded by the density of photogenerated polarons (~10^17 cm-3). The implications of these observations are discussed in relation to polymer/C60 photovoltaic cells

Conjugation-Length Dependence of Spin-Dependent Exciton Formation Rates in Pi-Conjugated Oligomers and Polymers

We have measured the ratio, r = $\sigma_S/\sigma_T$ of the formation cross section, $\sigma$ of singlet ($\sigma_S$) and triplet ($\sigma_T$) excitons from oppositely charged polarons in a large variety of $\pi$-conjugated oligomer and polymer films, using the photoinduced absorption and optically detected magnetic resonance spectroscopies. The ratio r is directly related to the singlet exciton yield, which in turn determines the maximum electroluminescence quantum efficiency in organic light emitting diodes (OLED). We discovered that r increases with the conjugation length, CL; in fact a universal dependence exists in which $r^{-1}$ depends linearly on $CL^{-1}$, irrespective of the chain backbone structure. These results indicate that $\pi$-conjugated polymers have a clear advantage over small molecules in OLED applications.Comment: 5 pages, 4 figure

Excitons in quasi-one dimensional organics: Strong correlation approximation

An exciton theory for quasi-one dimensional organic materials is developed in the framework of the Su-Schrieffer-Heeger Hamiltonian augmented by short range extended Hubbard interactions. Within a strong electron-electron correlation approximation, the exciton properties are extensively studied. Using scattering theory, we analytically obtain the exciton energy and wavefunction and derive a criterion for the existence of a $B_u$ exciton. We also systematically investigate the effect of impurities on the coherent motion of an exciton. The coherence is measured by a suitably defined electron-hole correlation function. It is shown that, for impurities with an on-site potential, a crossover behavior will occur if the impurity strength is comparable to the bandwidth of the exciton, corresponding to exciton localization. For a charged impurity with a spatially extended potential, in addition to localization the exciton will dissociate into an uncorrelated electron-hole pair when the impurity is sufficiently strong to overcome the Coulomb interaction which binds the electron-hole pair. Interchain coupling effects are also discussed by considering two polymer chains coupled through nearest-neighbor interchain hopping $t_{\perp}$ and interchain Coulomb interaction $V_{\perp}$. Within the $t$ matrix scattering formalism, for every center-of-mass momentum, we find two poles determined only by $V_{\perp}$, which correspond to the interchain excitons. Finally, the exciton state is used to study the charge transfer from a polymer chain to an adjacent dopant molecule.Comment: 24 pages, 23 eps figures, pdf file of the paper availabl