Theory of Exciton Migration and Field-Induced Dissociation in Conjugated Polymers

The interplay of migration, recombination, and dissociation of excitons in disordered media is studied theoretically in the low temperature regime. An exact expression for the photoluminescence spectrum is obtained. The theory is applied to describe the electric field-induced photoluminescence-quenching experiments by Kersting et al. [Phys. Rev. Lett. 73, 1440 (1994)] and Deussen et al. [Synth. Met. 73, 123 (1995)] on conjugated polymer systems. Good agreement with experiment is obtained using an on-chain dissociation mechanism, which implies a separation of the electron-hole pair along the polymer chain.Comment: 4 pages, RevTeX, 2 Postscript figure

Temperature and Field Dependence of the Mobility in Liquid-Crystalline Conjugated Polymer Films

The transport properties of organic light-emitting diodes in which the emissive layer is composed of conjugated polymers in the liquid-crystalline phase have been investigated. We have performed simulations of the current transient response to an illumination pulse via the Monte Carlo approach, and from the transit times we have extracted the mobility of the charge carriers as a function of both the electric field and the temperature. The transport properties of such films are different from their disordered counterparts, with charge carrier mobilities exhibiting only a weak dependence on both the electric field and temperature. We show that for spatially ordered polymer films, this weak dependence arises for thermal energy being comparable to the energetic disorder, due to the combined effect of the electrostatic and thermal energies. The inclusion of spatial disorder, on the other hand, does not alter the qualitative behaviour of the mobility, but results in decreasing its absolute value.Comment: 9 pages, 8 figures, submitted to Phys. Rev.

The size of electron-hole pairs in pi conjugated systems

We have performed momentum dependent electron energy-loss studies of the electronic excitations in sexithiophene and compared the results to those from parent oligomers. Our experiment probes the dynamic structure factor S(q,omega)and we show that the momentum dependent intensity variation of the excitations observed can be used to extract the size of the electron-hole pair created in the excitation process. The extension of the electron-hole pairs along the molecules is comparable to the length of the molecules and thus maybe only limited by structural constraints. Consequently, the primary intramolecular electron-hole pairs are relatively weakly bound. We find no evidence for the formation of excitations localized on single thiophene units.Comment: RevTex, 3 figures, to appear in Physical Review Letter

Theory of Electric Field-Induced Photoluminescence Quenching in Disordered Molecular Solids

The dynamics of excitons in disordered molecular solids is studied theoretically, taking into account migration between different sites, recombination, and dissociation into free charge carriers in the presence of an electric field. The theory is applied to interpret the results of electric field-induced photoluminescence (PL) quenching experiments on molecularly doped polymers by Deussen et al. [Chem. Phys. 207, 147 (1996)]. Using an intermolecular dissociation mechanism, the dependence of the PL quenching on the electric field strength and the dopant concentration, and the time evolution of the transient PL quenching can be well described. The results constitute additional proof of the distinct exciton dissociation mechanisms in conjugated polymer blends and molecularly doped polymers.Comment: 4 pages RevTeX, 3 Postscript figure

A theoretical investigation of the low lying electronic structure of poly(p-phenylene vinylene)

The two-state molecular orbital model of the one-dimensional phenyl-based semiconductors is applied to poly(p-phenylene vinylene). The energies of the low-lying excited states are calculated using the density matrix renormalization group method. Calculations of both the exciton size and the charge gap show that there are both Bu and Ag excitonic levels below the band threshold. The energy of the 1Bu exciton extrapolates to 2.60 eV in the limit of infinite polymers, while the energy of the 2Ag exciton extrapolates to 2.94 eV. The calculated binding energy of the 1Bu exciton is 0.9 eV for a 13 phenylene unit chain and 0.6 eV for an infinite polymer. This is expected to decrease due to solvation effects. The lowest triplet state is calculated to be at ca. 1.6 eV, with the triplet-triplet gap being ca. 1.6 eV. A comparison between theory, and two-photon absorption and electroabsorption is made, leading to a consistent picture of the essential states responsible for most of the third-order nonlinear optical properties. An interpretation of the experimental nonlinear optical spectroscopies suggests an energy difference of ca. 0.4 eV between the vertical energy and ca. 0.8 eV between the relaxed energy, of the 1Bu exciton and the band gap, respectively.Comment: LaTeX, 19 pages, 7 eps figures included using epsf. To appear in Physical Review B, 199

Ab-initio calculation of the electronic and optical excitations in polythiophene: effects of intra- and interchain screening

We present an calculation of the electronic and optical excitations of an isolated polythiophene chain as well as of bulk polythiophene. We use the GW approximation for the electronic self-energy and include excitonic effects by solving the electron-hole Bethe-Salpeter equation. The inclusion of interchain screening in the case of bulk polythiophene drastically reduces both the quasi-particle band gap and the exciton binding energies, but the optical gap is hardly affected. This finding is relevant for conjugated polymers in general.Comment: 4 pages, 1 figur

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

Electron correlation effects in electron-hole recombination in organic light-emitting diodes

We develop a general theory of electron--hole recombination in organic light emitting diodes that leads to formation of emissive singlet excitons and nonemissive triplet excitons. We briefly review other existing theories and show how our approach is substantively different from these theories. Using an exact time-dependent approach to the interchain/intermolecular charge-transfer within a long-range interacting model we find that, (i) the relative yield of the singlet exciton in polymers is considerably larger than the 25% predicted from statistical considerations, (ii) the singlet exciton yield increases with chain length in oligomers, and, (iii) in small molecules containing nitrogen heteroatoms, the relative yield of the singlet exciton is considerably smaller and may be even close to 25%. The above results are independent of whether or not the bond-charge repulsion, X_perp, is included in the interchain part of the Hamiltonian for the two-chain system. The larger (smaller) yield of the singlet (triplet) exciton in carbon-based long-chain polymers is a consequence of both its ionic (covalent) nature and smaller (larger) binding energy. In nitrogen containing monomers, wavefunctions are closer to the noninteracting limit, and this decreases (increases) the relative yield of the singlet (triplet) exciton. Our results are in qualitative agreement with electroluminescence experiments involving both molecular and polymeric light emitters. The time-dependent approach developed here for describing intermolecular charge-transfer processes is completely general and may be applied to many other such processes.Comment: 19 pages, 11 figure

Photoinduced absorption and photoluminescence in poly(2,5-dimethoxy-p- phenylene vinylene)

We report a study of the photoexcited states in the conjugated polymer poly(2,5-dimethoxy-p-phenylene vinylene). Photoluminescence due to radiative recombination of singlet excitons is observed at energiesjust below the onset of the pi-pi* absorption band at 2.1 eV. Photoinduced absorption at 80 K shows bands peaking at 0.68, 1.35, and 1.80 eV. The features at 0.68 and 1.8 eV are associated with the same excited state which we propose is a doubly charged bipolaron, while the third at 1.35 eV is unrelated. We assign this 1.35-eV absorption to a triplet-triplet transition of a triplet exciton. The bipolarons are long lived with significant numbers surviving in excess of 100 ms at 80 K, and have a weak temperature dependence such that photoinduced absorption is readily detectable even at room temperature. The triplet exciton has a lifetime of order 2.5 ms at 80 K but this falls rapidly at higher temperature and the response is not detected at room temperature. We contrast these results with those obtained previously for the related poly(arylene vinylene) polymers poly(p-phenylene vinylene), and poly(2,5-thienylene vinylene) and for other conjugated polymers, and draw attention to the important role played in the photophysics of these materials by neutral excited states

Ab-initio prediction of the electronic and optical excitations in polythiophene: isolated chains versus bulk polymer

We calculate the electronic and optical excitations of polythiophene using the GW approximation for the electronic self-energy, and include excitonic effects by solving the electron-hole Bethe-Salpeter equation. Two different situations are studied: excitations on isolated chains and excitations on chains in crystalline polythiophene. The dielectric tensor for the crystalline situation is obtained by modeling the polymer chains as polarizable line objects, with a long-wavelength polarizability tensor obtained from the ab-initio polarizability function of the isolated chain. With this model dielectric tensor we construct a screened interaction for the crystalline case, including both intra- and interchain screening. In the crystalline situation both the quasi-particle band gap and the exciton binding energies are drastically reduced in comparison with the isolated chain. However, the optical gap is hardly affected. We expect this result to be relevant for conjugated polymers in general.Comment: 15 pages including 4 figures; to appear in Phys. Rev. B, 6/15/200