A tandem mechanism of charge-carrier photogeneration in disordered organic materials

A model of tandem charge-carrier photogeneration in disordered organic materials at low excess photon energies above the absorption edge is formulated. It suggests that relaxed singlet excitons dissociate into strongly bound metastable short off-chain geminate pairs. In parallel, triplet excitons can be generated from both primary singlets and short geminate pairs. Owing to a long intrinsic lifetime of triplets, most of them are quenched by geminate pairs and the latter can gain additional energy that facilitates transformation of short pairs into longer ones. This reduces the Coulomb binding energy such that field-assisted full dissociation into free carriers becomes feasible.     

Charge carrier photogeneration in polymers

The charge carrier photogeneration in polymers can be depicted as a multistage process that involves i) photoexcitation to a neutral molecular electronic state, ii) autoionization of the excited state, iii) thermalization of the hot electron, leading to the formation of a Coulomb field-bound geminate electron-hole pair, and iv) thermal dissociation of the electron-hole pair into free carriers. This model is proposed for all types of polymers with a large ocnjugated pendant group and both the saturated and non-saturated main chain. The separation distance of the electron-hole pairs ranges from 2 to 3 nm, and the primary quantum efficiency of the electron-hole pairs formation assumes values of several tenths of charge per photon. In intrinsic materials like substituted polyacetylenes both the interchain and intrachain charge transfer excitons can be formed. Onsager's theory can provide a satisfactory explanation of the dissociation step. In polymers with the saturated main chain and large conjugated pendant groups the charge-transfer excitons are very often stabilized by self-trapping in dimer deep traps. Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday     

Poly(silyens)s: Charge Carrier Photogeneration and Transport: S. Nešpůrek,A. Eckhardt Polym. Adv. Technol. 12, 427–440 (2001)

The original article to which this Erratum refers was published in Polym. Adv. Technol. 12 , 427–440 (2001) In the following paragraph, ‘µ’ was inserted instead of ‘γ’. The paragraph should have read: Xerographic Discharge The electric field (F) dependences of photogeneration efficiency as measured by the xerographic discharge method are shown in Figure 4 for PMPSi and PBMSi. The electric field and temperature (T) dependences of the photogeneration efficiency can be described using Onsager theory of geminate recombination (full lines). This theory can be used to describe one step in the photogeneration process, the thermal dissociation of ion‐pairs formed by light into free charge carriers in the external electric field. Under the assumption that the distribution of bound pairs is spherically symmetrical, the overall photogeneration efficiency ν is expressed as where ?₀ is the voltage and temperature independent primary quantum yield (fraction of the ion‐pair generated per photon), g(r) is the spatial distribution of the pairs, and r is the pair separation distance. Function f(r,F,T) represents the Onsager dissociation probability [9] of the ion‐pair. The best theoretical fits of the experimental data given in Figure 4 were found using the Onsager theory with the Gaussian distribution of radii [17] ­ exp (?r²/γ²) using parameters: γ = 1.3 nm, η₀ = 0.45 and γ = 1.6 nm, η₀ = 0.85 for PMPSi and PBMSi, respectively. According to Eq. 2 the photogeneration quantum efficiency η is also temperature dependent. The activation energy was determined as E_η = 0.05 eV for PMPSi (inset in Figure 4) and 0.04 eV for PBMSi. The temperature dependence of the photogeneration efficiency is also in good agreement with the Onsager dissociation theory (full line in inset of Figure 4).     

Field-dependent photogeneration in molecularly doped polymers

The photogeneration of holes in triphenylamine- doped polycarbonate, polystyrene, polyvinyl butyral has been investigated. The field dependence of the photogeneration efficiencies can be explained by the Onsager theory of geminate recombination. The results show that the number of bound electron-hole pairs that are formed per absorbed photon is strongly dependent on the polymer composition whereas the pair disassociation probability is independent of the polymer.     

The effect of solvent additives on morphology and excited-state dynamics in PCPDTBT:PCBM photovoltaic blends

The dependence of the thin film morphology and excited-state dynamics for the low-bandgap donor-acceptor copolymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) in pristine films and in blends (1:2) with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) on the use of the solvent additive 1,8-octanedithiol (ODT) is studied by solid-state nuclear magnetic resonance (NMR) spectroscopy and broadband visible and near-infrared pump-probe transient absorption spectroscopy (TAS) covering a spectral range from 500-2000 nm. The latter allows monitoring of the dynamics of excitons, bound interfacial charge-transfer (CT) states, and free charge carriers over a time range from femto- to microseconds. The broadband pump-probe experiments reveal that excitons are not only generated in the polymer but also in PCBM-rich domains. Depending on the morphology controlled by the use of solvent additives, polymer excitons undergo mainly ultrafast dissociation (<100 fs) in blends prepared without ODT or diffusion-limited dissociation in samples prepared with ODT. Excitons generated in PCBM diffuse slowly to the interface in both samples and undergo dissociation on a time scale of several tens of picoseconds up to hundreds of picoseconds. In both samples a significant fraction of the excitons creates strongly bound interfacial CT states, which exhibit subnanosecond geminate recombination. The total internal quantum efficiency loss due to geminate recombination is estimated to be 50% in samples prepared without ODT and is found to be reduced to 30% with ODT, indicating that more free charges are generated in samples prepared with solvent additives. In samples prepared with ODT, the free charges exhibit clear intensity-dependent recombination dynamics, which can be modeled by Langevin-type recombination with a bimolecular recombination coefficient of 6.3 × 10(-11) cm(3) s(-1). In samples prepared without ODT, an additional nanosecond recombination of polaron pairs is observed in conjunction with an increased intensity-independent trap-assisted nongeminate recombination of charges. Furthermore, a comparison of the triplet-induced absorption spectra of PCPDTBT with the charge-induced absorption in PCPDTBT:PCBM blends reveals that triplets have a very similar excited-state absorption spectrum compared to the free charge carriers, however, in contrast have a distinct intensity-independent lifetime. Overall, our results suggest that whether free charges or strongly bound CT states are created upon dissociation of excitons at the PCPDTBT:PCBM interface is determined instantaneously upon exciton dissociation and that once formed strongly bound CT states rapidly recombine and thus are unlikely to dissociate into free charges. The observation of a significantly larger bimolecular recombination coefficient than previously determined for poly(3-hexylthiophen-2,5-diyl):PCBM (P3HT:PCBM) and PCDTBT:PCBM samples indicates that nongeminate recombination of free charges considerably competes with charge extraction in PCPDTBT:PCBM photovoltaic devices.     

Geminate charge recombination in alternating polyfluorene copolymer/fullerene blends

By measuring excited state and charge dynamics in blends of an alternating polyfluorene copolymer and fullerene derivative over nine orders in time and two orders in light intensity, we have monitored the light-induced processes from ultrafast charge photogeneration to much slower decay of charges by recombination. We find that at low light intensities relevant to solar cell operation relatively fast (approximately 30 ns) geminate recombination is the dominating charge decay process, while nongeminate recombination has a negligible contribution. The conclusion of our work is that under solar illumination conditions geminate recombination of charges may be directly competing with efficient charge collection in polymer/fullerene solar cells.     

A study of carrier generation in β-metal-free phthalocyanine

Photoinduced carrier generation has been studied in particle dispersions of β-metal-free phthalocyanine purified by temperature gradient sublimation. In addition to the photoconductive response measured by the delayed-collection-field technique, electric-field-induced fluorescence quenching and delayed fluorescence were also investigated. The results are consistent with the model which assumes that carrier generation proceeds through an intermediate, charge transfer (CT) state, which either dissociates into free carriers or predominantly decays to the ground state. Delayed-collection field and delayed-fluorescence experiments show that the geminate electron-hole pair is very long lived (tens of milliseconds) and has a non-exponential time decay. These results represent a new evidence for the observation of time-resolved carrier generation first reported by Mort et al. in polyvinyl carbazole. Field dependence of the geminate electron-hole pair dissociation yield is consistent with the Poole-Frenkel mechanism.     

Ultrafast charge photogeneration dynamics in ground-state charge-transfer complexes based on conjugated polymers

The charge photogeneration and early recombination in MEH-PPV-based charge-transfer complexes (CTCs) and in MEH-PPV/PCBM blend as a reference are studied by ultrafast visible-pump-IR-probe spectroscopy. After excitation of the CTC band, an immediate (<100 fs) electron transfer is observed from the polymer chain to the acceptor with the same yield as in the MEH-PPV/PCBM blend. The forward charge transfer in the CTCs is followed by an efficient (approximately 95%) and fast (<30 ps) geminate recombination. For comparison, the recombination efficiency obtained in the MEH-PPV/PCBM blend does not exceed a mere 50%. Polarization-sensitive experiments demonstrate high (approximately 0.3) values of transient anisotropy for the CTCs polaron band. In contrast, in the MEH-PPV/PCBM blend the dipole moment orientation of the charge-induced transition is less correlated with the polarization of the excitation photon. According to these data, photogeneration and recombination of charges in the CTCs take place locally (i.e., within a single pair of a polymer conjugation segment and an acceptor) while in the MEH-PPV/PCBM blend exciton migration precedes the separation of charges. Results of the ultrafast experiments are supported by photocurrent measurements on the corresponding MEH-PPV/acceptor photodiodes.     

Magnetic field effects on spin-rephasing in a photochemically produced radical pair investigated by a double-pulse technique using a nitrogen laser

The effect of an external magnetic field on the yield of the benzophenone ketyl radical has been investigated by a new, double-pulse technique. The technique and its variants can be used not only for studying geminate recombination of photochemically produced radical pairs but also for continuous photoelectric recording of fluorescence spectra of the free radicals which can be generated by nitrogen laser irradiation.     

Picosecond kinetic study of the photoinduced homolysis of benzhydryl acetates: the nature of the conversion of radical pairs into ion pairs

The conversion of benzhydryl acetate geminate radical pairs to contact ion pairs following photoinduced homolysis in solution is studied using picosecond pump-probe spectroscopy. The dynamics for the decay of the geminate radical pairs into contact ion pairs is modeled within a Marcus-like theory for nonadiabatic electron transfer. A second decay channel for the geminate radical pairs is diffusional separation to free radicals. The kinetics of this latter process reveals an energy of interaction between the two radicals in the geminate pair.     

Monte-Carlo simulations of geminate electron–hole pair dissociation in a molecular heterojunction: a two-step dissociation mechanism

The Monte-Carlo simulations are used to investigate the dissociation of a Coulomb correlated charge pair at an idealized interface between an electron accepting and an electron donating molecular material. In the simulations the materials are represented by cubic lattices of sites, with site the energies spread according to Gaussian distributions. The influence of temperature, applied external fields, and the width of the Gaussian densities of states distribution for both the electron and the hole transporting material are investigated. The results show that the dissociation of geminate charge pairs is assisted by disorder and the results can be understood in terms of a two-step model. In the first step, the slow carrier in the most disordered material jumps away from the interface. In the following, second step, the reduced Coulombic attraction allows the faster carrier in the less disordered material to escape from the interface by thermally activated hopping. When the rate for geminate recombination at the interface is very low (<1 ns⁻¹) the simulations predict a high yield for carrier collection, as observed experimentally. Comparison of the simulated and experimentally observed temperature dependence of the collection efficiency indicates that at low temperature dissociation of the geminate charge pairs may be one of the factors limiting the device performance.     

Photophysics of an electrophosphorescent platinum (II) porphyrin in solid films

We examine electronic processes in platinum (II) octaethyl porphyrin (PtOEP) embedded in an organic solid state matrix and in the form of vacuum-evaporated neat films in conjunction with potential applications of this compound to organic photovoltaic and electrophosphorescent devices. Absorption, photoexcitation, and luminescence spectra indicate the excitonic dimers to be dominant excited states, and their dissociation underlies the charge photogeneration process. Different charge separation distance (1.5 nm and 2.6 nm) in opposite charge carrier pairs preceding dissociation can be distinguished based on the fit of the three-dimensional Onsager theory of geminate recombination to electromodulated luminescence and photoconduction measurements. The near-positive electrode concentrated triplet dimer excitons, produced by strongly 370 nm absorbed light in neat PtOEP films, are efficiently quenched by electron transfer to the metal (Al), generating the positive charge with an efficiency eta+ exceeding 0.15 at high electric fields and dominating the measured photocurrent. Their dissociation efficiency in the bulk, eta- (negatively biased illuminated electrode), is more than one order of magnitude lower than eta+. The dissociation of singlet dimer states dominates the bulk photogeneration process induced by the weakly-absorbed light at 450 nm, with comparable eta+ and eta-. The "hot excited state" underlying the temperature-increasing emission at 540 nm has been attributed to the upper excitonic component Q+ of the first absorption band Q consistent with the exciton concept applied successfully to the interpretation of all dimer-underlain spectroscopic features of PtOEP samples studied.     

Dynamic Monte Carlo modeling of exciton dissociation in organic donor-acceptor solar cells

A general dynamic Monte Carlo model for exciton dissociation at a donor-acceptor interface that includes exciton delocalization and hot charge separation is developed to model the experimental behavior observed for the poly(3-hexylthiophene):fullerene system and predict the theoretical performance of future materials systems. The presence of delocalized excitons and the direct formation of separated charge pairs has been recently measured by transient photo-induced absorption experiments and has been proposed to facilitate charge separation. The excess energy of the exciton dissociation process has also been observed to have a strong correlation with the charge separation yield for a series of thiophene based polymer:fullerene systems, suggesting that a hot charge separation process is also occurring. Hot charge separation has been previously theorized as a cause for highly efficient charge separation. However, a detailed model for this process has not been implemented and tested. Here, both conceptual models are implemented into a dynamic Monte Carlo simulation and tested using a simple bilayer donor-acceptor system. We find that exciton delocalization can account for a significant reduction in geminate recombination when compared to the traditional, bound polaron pair model. In addition, the hot charge separation process could further reduce the geminate recombination, but only if the hot charge mobility is several orders of magnitude larger than the standard charge mobility.     

Electron-transfer fluorescence quenching of aromatic hydrocarbons by europium and ytterbium ions in acetonitrile

To make the effects of molecular size on photoinduced electron-transfer (ET) reactions clear, the ET fluorescence quenching of aromatic hydrocarbons by trivalent lanthanide ions M3+ (europium ion Eu3+ and ytterbium ion Yb3+) and the following ET reactions such as the geminate and free radical recombination were studied in acetonitrile. The rate constant k(q) of fluorescence quenching, the yields of free radical (phi(R)) and fluorescer triplet (phi(T)) in fluorescence quenching, and the rate constant k(rec) of free radical recombination were measured. Upon analysis of the free energy dependence of k(q), phi(R), phi(T), and k(rec), it was found that the switchover of the fluorescence quenching mechanism occurs at deltaG(fet) = -1.4 to -1.6 eV: When deltaG(fet) < -1.6 eV, the fluorescence quenching by M3+ is induced by a long-distance ET yielding the geminate radical ion pairs. When deltaG(fet) > -1.4 eV, it is induced by an exciplex formation. The exciplex dissociates rapidly to yield either the fluorescer triplet or the geminate radical ion pairs. The large shift of switchover deltaG(fet) from -0.5 eV for aromatic quenchers to -1.4 to -1.6 eV for lanthanide ions is almost attributed to the difference in the molecular size of the quenchers. Furthermore, it was substantiated that the free energy dependence of ET rates for the geminate and free radical recombination is satisfactorily interpreted within the limits of the Marcus theory.     

Photoinduced bimolecular electron transfer investigated by femtosecond time-resolved infrared spectroscopy

Ultrafast infrared transient absorption spectroscopy is used to study the photoinduced bimolecular electron transfer reaction between perylene in the first singlet excited state and 1,4-dicyanobenzene in acetonitrile and dichloromethane. Following vibrational marker modes on both donor and acceptor sides in real time provides direct insight into the structural dynamics during the reaction. A band narrowing on a time scale of a few tens of picoseconds observed on the antisymmetric CN stretching vibration of the dicyanobenzene radical anion indicates that a substantial part of the excess energy is channeled into vibrational modes of the product, despite the fact that the reaction is weakly exergonic. An additional narrowing of the same band on a time scale of several hundreds of picoseconds observed in acetonitrile only is interpreted as a signature of the dissociation of the geminate ion pairs into free ions.     

Influence of the interaction of chromophores of bis-cyanine dyes on the photogeneration of charge carriers in poly-N-epoxypropylcarbazole films

An increase in photoconductivity and in the extinguishing effect of an external electric field has been observed in the photoluminescence of doped poly-N-epoxypropylcarbazole films on changing from cyanine dyes with normal chromophores to the corresponding bis-cyanines. It was concluded that an increase in photogeneration of triplet electron-hole pairs arose with such replacement of the dye and that dissociation of the pairs was responsible for the photoconductivity. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 6, pp. 371–375, November–December, 1998.     

From molecular chemistry to supramolecular chemistry to superdupermolecular chemistry. Controlling covalent bond formation through non-covalent and magnetic interactions

The reactions of carbon centered radical pairs often involve diffusion controlled combination and/or disproportionation reactions which are non-selective. A triplet geminate pair of radicals is produced by the photolysis of suitable ketones. The reactions of such geminate pairs can be controlled though the application of supramolecular concepts which emphasize non-covalent interaction to "steer" the geminate pair toward a selected pathway. In addition, "superdupermolecular" concepts, which emphasize the control of radical pair reactions through the orientation of electron spins, can be employed to further control the course of geminate pair reactions. Examples of control of a range of the selectivity of geminate radical combinations, which form strong covalent bonds, through supramolecular and superdupermolecular effects will be presented for the photolysis of ketones adsorbed in the supercages of zeolites.     

Electric field dependence of charge carrier generation in alkane solutions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD)

Studies of the electric field dependence or photocurrents from solutions of TMPD in non-polar solvents are interpreted using Onsager's theory of geminate charge recombination. For all solvents and photon energies, a simple exponential form of the radial distribution function for geminate pairs accounts for the observed field dependence.     

Spin dynamic study on the electric field dependence of carrier generation

Using an acceptor-doped poly(N-vinylcarbazole) film, the magnetic field effect (MFE) on the generation efficiency of photoinduced charge was measured under various electric fields in order to clarify how the applied electric field affects the elementary processes in the photocarrier generation in photoconductive polymeric molecular solids. The external magnetic field influenced the electron spin dynamics among the geminate electron-hole pairs within a scale of a few nanometers and decreased the photocarrier generation efficiency. The observed MFE due to a hyperfine mechanism was almost independent of the electric field. By employing the stochastic Liouville equations based on a one-dimensional lattice model, we performed some model calculations for the dissociation, hopping, and recombination rate dependence of MFE on the generation efficiency. From a comparison between the observed and calculated MFE, it was concluded that the electric field affects the dissociation more than the hopping and the recombination. This coincides with the concepts in the Onsager model that is used to analyze the electric field dependence of carrier generation efficiency so far. The one-dimensional lattice model is a proper model for the carrier generation in polymeric molecular solids, which is qualitatively consistent with the Onsager model except for the long-range hole jump.