Here, a general experimental method to determine the energy ECT of intermolecular charge‐transfer (CT) states in electron donor–acceptor (D–A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D–A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open‐circuit voltage (Voc) of photovoltaic devices in D–A blends via eVoc = ECT − 0.5 eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1 → CT) occurs when Eg − ECT > 0.1 eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT → T1) can occur when ECT − ET > 0.1 eV. From these relations, it is concluded that in D–A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc = Eg − 0.6 eV) and ii) the singlet–triplet energy gap should be ΔEST < 0.2 eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area.

The electro-optical properties of thin films of electron donor-acceptor blends of a fluorene copolymer (PF10TBT) and a fullerene derivative (PCBM) were studied. Transmission electron microscopy shows that in these films nanocrystalline PCBM clusters are formed at high PCBM content. For all concentrations, a charge transfer (CT) transition is observed with absorption spectroscopy, photoluminescence, and electroluminescence. The CT emission is used as a probe to investigate the dissociation of CT excited states at the donor-acceptor interface in photovoltaic devices, as a function of an applied external electric field and PCBM concentration. We find that the maximum of the CT emission shifts to lower energy and decreases in intensity with higher PCBM content. We explain the red shift of the emission and the lowering of the open-circuit voltage (V(OC)) of photovoltaic devices prepared from these blends with the higher relative permittivity of PCBM (epsilon(r) = 4.0) compared to that of the polymer (epsilon(r) = 3.4), stabilizing the energy (E(CT)) of CT states and of the free charge carriers in blends with higher PCBM concentration. We show that the CT state has a short decay time (tau = ca. 4 ns) that is reduced by the application of an external electric field or with increasing PCBM content. The field-induced quenching can be explained quantitatively with the Onsager-Braun model for the dissociation of the CT states when including a high electron mobility in nanocrystalline PCBM clusters. Furthermore, photoinduced absorption spectroscopy shows that increasing the PCBM concentration reduces the yield of neutral triplet excitons forming via electron-hole recombination, and increases the lifetime of radical cations. The presence of nanocrystalline domains with high local carrier mobility of at least one of the two components in an organic heterojunction may explain efficient dissociation of CT states into free charge carriers.

Comparative studies on hydrogen-bonded versus covalently linked donor-acceptor-donor dye arrays obtained from oligo(p-phenylene vinylene)s (OPVs) as donor and bay-substituted perylene bisimides (PERYs) as acceptor dyes are presented. Both systems form well-ordered J-type aggregates in methylcyclohexane, but only hydrogen-bonded arrays afford hierarchically assembled chiral OPV-PERY dye superstructures consisting of left-handed helical pi-pi co-aggregates (CD spectroscopy) of the two dyes that further assemble into right-handed nanometer-scale supercoils in the solid state (AFM study). In the case of hydrogen-bonded arrays, the stability of the aggregates in solution increases with increasing conjugation length of the OPV unit. The well-defined co-aggregated dyes presented here exhibit photoinduced electron transfer on subpicosecond time scale, and thus, these supramolecular entities might serve as valuable nanoscopic functional units.

cyclic voltammograms were taken for these two carbons by varying the scan rate from 5 mV/s to 50 mV/s, the SNU-2 carbon kept the rectangular-shape up to a scan rate of 20 mV/s (Fig. 5b, solid line). In contrast, the MSC-25 carbon showed a deformed cyclic voltammogram at a scan rate of 10 mV/s and a completely collapsed one at a scan rate of 20 mV/s (Fig. 5b, dotted line). A detailed discussion on the electrochemical studies of the material will be presented in a forthcoming paper.In conclusion, we have made a new high surface area mesoporous carbon using Al-HMS as a template. From this research we discovered that the pores of HMS are 3D interconnected, unlike the originally proposed disordered hexagonal structure. The EDLC performance of the carbon material was superior to the commercially available carbon MSC-25 due to improved mesoporosity. The CV of the mesoporous carbon showed ideal rectangular shapes at a high scan rate of 20 mV/s.

We demonstrate a facile route to obtain high and broad-band circular polarization of electroluminescence in single-layer polymer OLEDs. As a light-emitting material we use a donor-acceptor polyfluorene with enantiomerically pure chiral side-chains. We show that upon thermal annealing the polymer self-assembles into a multidomain cholesteric film. By varying the thickness of the polymer emitting layer, we achieve high levels of circular polarization of electroluminescence (up to 40% excess of right-handed polarization), which are the highest reported for polymer OLEDs not using chiral dopants or alignment layers. Mueller matrix ellipsometry shows strong optical anisotropies in the film, indicating that the circular polarization of luminescence arises mainly after the photon has been generated, through selective scattering and birefringence correlated in the direction of the initial linear polarization of the photon. Our work demonstrates that chirally substituted conjugated polymers can combine photonic and semiconducting properties in advanced optoelectronic devices.

Photoexcitations in helical aggregates of a functionalized, chiral oligophenylenevinylene (MOPV) are described going beyond the Born-Oppenheimer approximation, in the form of dressed (polaronic) Frenkel excitons. This allows for accurate modeling of the experimentally observed wavelength dependence of the circular polarization in fluorescence, which directly probes the non-adiabatic nature of the electron-vibration (EV) coupling in this system. The fluorescence photon is emitted from a nuclear geometry in which one MOPV and its two nearest neighbors have a nuclear equilibrium that differs appreciably from the ground state due to the presence of the excited state. The absorption and emission band shape and the circular dichroism are consistent with a coherence range of the emitting excitation of approximately two neighboring molecules. Random fluctuations in the zero-order excited-state energy of the MOPVs (disorder) limit the exciton delocalization and can be described by a Gaussian distribution of energies with a width sigma=0.12 eV and a spatial correlation length l0 approximately 5 molecules. We find that disorder and EV coupling act synergistically in localizing the emitting exciton to a single MOPV in the aggregate with 95% probability.

The nature of the solubilizing alkyl side chains has a strong effect on the performance of semiconducting diketopyrrolopyrrole polymers in organic solar cells with fullerene acceptors. The effect relates to the width of semicrystalline polymer fibrils that form in these blends. If the width of the fibril is wider than the exciton diffusion length, fewer charges form and the efficiency drops.

The use of diiodooctane as processing additive for construction of PCPDTBT:PCBM solar cells results in a profound change in photophysical behavior of this blend. In the improved morphology obtained with the additive, recombination of charge carriers to the lowest triplet excited state is suppressed. This contributes to the boost in solar power conversion efficiency induced by the use of the processing agent.