What is the Binding Energy of a Charge Transfer State in an Organic Solar Cell?

The high efficiencies reported for organic solar cells and an almost negligible thermal activation measured for the photogeneration of charge carriers have called into question whether photoinduced interfacial charge transfer states are bound by a significant coulomb attraction, and how this can be reconciled with very low activation energies. Here, this question is addressed in a combined experimental and theoretical approach. The interfacial binding energy of a charge‐transfer state in a blend of MeLPPP:PCBM is determined by using energy resolved electrochemical impedance spectroscopy and is found to be about 0.5 eV. Temperature‐dependent photocurrent measurements on the same films, however, give an activation energy that is about one order of magnitude lower. Using analytical calculations and Monte Carlo simulation the authors illustrate how i) interfacial energetics and ii) transport topology reduce the activation energy required to separate the interfacial electron–hole pair, with about equal contributions from both effects. The activation energy, however, is not reduced by entropy, although entropy increases the overall photodissociation yield.     

The development of molecular fluorescent switches

Molecular systems in which fluorescence switches between 'on' and 'off' states when driven by chemical stimuli can be designed according to a few principles. The photochemical mechanisms examined are photoinduced electron transfer, internal charge transfer and excimer formation, with emphasis on the first category. These designs open the way to sharp signalling of small chemical species that perform critical biological functions.     

Ion-responsive supramolecular fluorescent systems based on multichromophoric calixarenes: A review

Calixarenes are useful building platforms in the design of multichromophoric systems in which photoinduced phenomena (electron, charge and proton transfers, excimer formation and resonance energy transfer) are controlled by ions. The applications mainly concern ion sensing with high selectivity.     

Optical Properties of Organic Semiconductor Blends with Near‐Infrared Quantum‐Dot Sensitizers for Light Harvesting Applications

We report an optical investigation of conjugated polymer (P3HT)/fullerene (PCBM) semiconductor blends sensitized by near‐infrared absorbing quantum dots (PbS QDs). A systematic series of samples that include pristine, binary and ternary blends of the materials are studied using steady‐state absorption, photoluminescence (PL) and ultrafast transient absorption. Measurements show an enhancement of the absorption strength in the near‐infrared upon QD incorporation. PL quenching of the polymer and the QD exciton emission is observed and predominantly attributed to intermaterial photoinduced charge transfer processes. Pump‐probe experiments show photo‐excitations to relax via an initial ultrafast decay while longer‐lived photoinduced absorption is attributed to charge transfer exciton formation and found to depend on the relative ratio of QDs to P3HT:PCBM content. PL experiments and transient absorption measurements indicate that interfacial charge transfer processes occur more efficiently at the fullerene/polymer and fullerene/nanocrystal interfaces compared to polymer/nanocrystal interfaces. Thus the inclusion of the fullerene seems to facilitate exciton dissociation in such blends. The study discusses important and rather unexplored aspects of exciton recombination and charge transfer processes in ternary blend composites of organic semiconductors and near‐infrared quantum dots for applications in solution‐processed photodetectors and solar cells.     

Photoinduced electron transfer through the hydrocarbon zone of membranes at low temperatures

The photoinduced electron transfer at low temperatures in phospholipide membranes (liposomes) containing chlorophyll and 3 X 10-docsilpalmitate has been investigated. The reduction of 3 X 10-docsilpalmitate was estimated by ESR spectrometry. When diffusion movement of the molecules in membranes was blocked by low temperatures the photoinduced electron transfer has been found. The mechanism of these phenomena were analyzed on the base of donor-acceptor interaction through sigma bonds in hydrocarbon bridged donor-acceptor complexes. The separation of charges in these complexes is regarded as occurs by the migration of a hole along the hydrocarbon system. An approximate estimate of the charge mobility in the saturated hydrocarbon side chain of chlorophyll and activation energy of these movement was obtained.     

Exploring the Conformational Behavior of Rigid Porphyrin-Quinone Systems by High-Temperature MD Simulations and Temperature-Dependent 1H-NMR Experiments

Photoinduced electron transfer reactions play an important role in the primary step of the biological photosynthesis process. In an attempt to understand better the mechanism of the charge separation organic donor-acceptor molecules containing porphyrins and quinones were designed as photosynthesis models. In order to study the structure dependence of the photoinduced electron transfer twofold and fourfold bridged porphyrin-quinone systems with increasing donor-acceptor distance were synthesized (Figure 1) [1, 2, 3]. It was assumed that in these molecules the porphyrin and quinone should be linked in a rigid and well-defined orientation. To verify this assumption the conformational behavior of these systems was studied by high-temperature MD simulations in combination with conformational analysis of selected minimized structures [4, 5].     

A Comparison of Five Experimental Techniques to Measure Charge Carrier Lifetime in Polymer/Fullerene Solar Cells

It is important to accurately measure the charge carrier lifetime, a crucial parameter that influences the collection efficiency in organic solar cells. Five transient and small perturbation experimental techniques that measure charge carrier lifetime are applied to a device composed of the polymer PDTSiTTz blended with the fullerene PCBM: time‐resolved charge extraction (TRCE), transient absorption spectroscopy (TAS), photoinduced charge extraction by linearly increasing voltage (photo‐CELIV), transient photovoltage, and electrochemical impedance spectroscopy. The motivation is to perform a comprehensive comparison of several different lifetime measurement techniques on the same device in order to assess their relative accuracy, applicability to operational devices, and utility in data analysis. The techniques all produce similar charge carrier lifetimes at high charge densities, despite previous suggestions that transient methods are less accurate than small perturbation ones. At lower charge densities an increase in the apparent reaction order is observed. This may be related to surface recombination at the contacts beginning to dominate, or an inhomogeneous charge distribution. A combination of TAS and TRCE appears suitable. TAS enables the investigation of recombination mechanisms at early times since it is not limited by RC (resistance‐capacitance product) or charge extraction losses. Conversely, TRCE is useful particularly at low densities when other mechanisms, such as surface recombination, may occur.     

From complexation to computation: Recent progress in molecular logic

The new thrusts in molecular logic are gathered together in this short review, while paying attention to the seeds from which these developments have arisen. The original demonstration of a few basic logic operations has now been extended to cover many of the one- and two-input varieties and even some of the three-input types. Many kinds of inputs and outputs have emerged, including various chemical species and some physical properties. The latter can include heat, light and, arguably, polarity. Reconfigurable logic has grown up to include a range of examples. Even superposable logic has proved possible with molecular systems. Numerical processors have flowered in recent years with several diverse approaches being revealed in recent years. Photochemical concepts such as photoinduced electron transfer (PET), internal charge transfer (ICT) and electronic energy transfer (EET) can be discerned among the designs in the field.     

Enhancement of VOC without Loss of JSC in Organic Solar Cells by Modification of Donor/Acceptor Interfaces

Organic solar cells (OSCs) are promising low‐cost devices for generating electricity. In addition to fill factor, the short circuit current density (J_SC) and the open circuit voltage (V_OC) are two key factors that have critical influence on the device performance. The energy levels of the donor and acceptor materials are crucial for achieving a high J_SC and V_OC. However, the interfacial structures between the organic materials substantially affect the J_SC and V_OC through the energy of the charge transfer (CT) states and the charge separation and recombination reaction kinetics. Here, it is reported that separating the donor and acceptor layer in bilayer OSCs with a thin insulating layer increases the energy of the CT state by weakening the Coulomb interaction at the interface and this also suppresses photoinduced CT and recombination. Although these effects usually increase V_OC and decrease J_SC, the trade‐off is avoided by doping the insulating layer with a dye to utilize the energy transfer process. The increase in V_OC without the reduction in J_SC enhances the conversion efficiency of the OSCs by 30%.     

The medium reorganization energy for the charge transfer reactions in proteins

A low static dielectric permittivity of proteins causes the low reorganization energies for the charge transfer reactions inside them. This reorganization energy does not depend on the pre-existing intraprotein electric field. The charge transferred inside the protein interacts with its aqueous surroundings; for many globular proteins, the effect of this surroundings on the reorganization energy is comparable with the effect of reorganization of the protein itself while for the charge transfer in the middle of membrane the aqueous phase plays a minor role. Reorganization energy depends strongly on the system considered, and hence there is no sense to speak on the "protein reorganization energy" as some permanent characteristic parameter. We employed a simple algorithm for calculation of the medium reorganization energy using the numerical solution of the Poisson-Boltzmann equation. Namely, the reaction field energy was computed in two versions - all media having optical dielectric permittivity, and all the media with the static one; the difference of these two quantities gives the reorganization energy. We have calculated reorganization energies for electron transfer in cytochrome c, various ammine-ruthenated cytochromes c, azurin, ferredoxin, cytochrome c oxidase, complex of methylamine dehydrogenase with amicyanin, and for proton transfer in α-chymotrypsin. It is shown that calculation of the medium reorganization energy can be a useful tool in analysis of the mechanisms of the charge transfer reactions in proteins.     

Charge Photogeneration in Organic Photovoltaics: Role of Hot versus Cold Charge‐Transfer Excitons

The role of excess excitation energy on long‐range charge separation in organic donor/acceptor bulk heterojunctions (BHJs) continues to be unclear. While ultrafast spectroscopy results argue for efficient charge separation through high‐energy charge‐transfer (CT) states within the first picosecond (ps) of excitation, charge collection measurements suggest excess photon energy does not increase the current density in BHJ devices. Here, the population dynamics of charge‐separated polarons upon excitation of high‐energy polymer states and low‐energy interfacial CT states in two polymer/fullerene blends from ps to nanosecond time scales are studied. It is observed that the charge‐separation dynamics do not show significant dependence on excitation energy. These results confirm that excess exciton energy is not necessary for the effective generation of charges.     

The role of structural reorganization in charge carrier transfer in DNA molecule

A model of hole transfer in DNA molecules has been proposed, which takes into account changes in the reorganization energy and orbital coupling between the neighboring bases during the charge transfer in different molecular sequences. It is shown that the rate of hole transfer by the superexchange and hopping transfer mechanisms is limited by the relaxation of the geometries of nucleobases participating in charge migration and the dynamics of solvent molecules. The rate of charge transfer in the DNA molecule is found to be dependent on the height of the potential barriers between the nucleotide and the molecular sequences. The inclusion of the interchain charge transfer, which is characterized by weak coupling between the nucleotides located in opposite strands, does not affect the general charge transport in DNA. The increase in the number of the parallel components of the hopping mechanism leads to a rise in the charge transfer rate in the double helix.     

Photoinduced electron transfer and energy transfer reactions of hydroxo-(2,2′:6′,2″-terpyridine) platinum(II)

The luminescent complex [Pt(terpy)OH]BF₄ undergoes photoinduced electron transfer reactions with phenyl amine electron donors and nitrophenyl electron acceptors. Stern-Volmer analysis of the quenching of metal-to-ligand charge transfer phosphorescence (³MLCT) was used to calculate bimolecular rate constants for electron transfer. Rate constants vary from 10⁸ to >10¹⁰ M⁻¹ s⁻¹, depending on the thermodynamic driving force of the electron transfer reaction, with rate constants indicating that [Pt(terpy)OH]BF₄* is a powerful photo-oxidant. Aromatic triplet energy acceptors can also quench the ³MLCT emission.     

Simultaneous Open‐Circuit Voltage Enhancement and Short‐Circuit Current Loss in Polymer: Fullerene Solar Cells Correlated by Reduced Quantum Efficiency for Photoinduced Electron Transfer

The limits of maximizing the open‐circuit voltage V_oc in solar cells based on poly[2,7‐(9,9‐didecylfluorene)‐alt‐5,5‐(4,7‐di‐2‐thienyl‐2,1,3‐benzothiadiazole)] (PF10TBT) as a donor using different fullerene derivatives as acceptor are investigated. Bulk heterojunction solar cells with PF10TBT and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) give a V_oc over 1 V and a power conversion efficiency of 4.2%. Devices in which PF10TBT is blended with fullerene bisadduct derivatives give an even higher V_oc, but also a strong decrease in short circuit current (J_sc). The higher V_oc is attributed to the higher LUMO of the acceptors in comparison to PCBM. By investigating the photophysics of PF10TBT:fullerene blends using near‐IR photo‐ and electroluminescence, time‐resolved photoluminescence, and photoinduced absorption we find that the charge transfer (CT) state is not formed efficiently when using fullerene bisadducts. Hence, engineering acceptor materials with a LUMO level that is as high as possible can increase V_oc, but will only provide a higher power conversion efficiency, when the quantum efficiency for charge transfer is preserved. To quantify this, we determine the CT energy (E_CT) and optical band gap (E_g), defined as the lowest first singlet state energy E_S1 of either the donor or acceptor, for each of the blends and find a clear correlation between the free energy for photoinduced electron transfer and J_sc. We find that E_g ? qV_oc > 0.6 eV is a simple, but general criterion for efficient charge generation in donor‐acceptor blends.     

Semiempirical MNDO/ZINDO study of linker effects on charge transfer in nitrobenzyl-substituted tetramethyl-fulvalenes

Semiempirical MNDO and ZINDO calculations have been performed to investigate the ground states of the neutral molecules and mono- and di-cations of nitrobenzyl-substituted tetramethylfulvalene (TMF), tetramethyl-tetrahydrofulvalene (TMTHF), and tetramethyl-tetrathiafulvalene (TMTTF). In particular, the effects of the linker groups on the direct charge transfer between the fulvalene and the nitrobenzyl groups have been studied. As linkers,-(CH₂)₂-, -CH₂O-,-CH₂S-, and -CO- were used. The coefficients of the highest occupied and lowest unoccupied molecular orbitals, the oscillator strengths and excited-state dipole moments for the vertical excitations from the neutral ground states, as obtained with SCI calculations, are reported. Although the dipole moments increase by 40–50 D when exciting from the HOMO localized on the fulvalene fragment to the LUMO localized on the nitrobenzyl part, all four linkers are found to be good insulators and thus, no direct optical donor to acceptor charge transfer can be observed. An alternative route, the photoinduced charge transfer process involving local excitations to form metastable intermediate states, is discussed. Due to the insulating properties of the linkers, these will then efficiently stabilize the charge transfer complex.     

Spontaneous Exciton Dissociation at Organic Semiconductor Interfaces Facilitated by the Orientation of the Delocalized Electron–Hole Wavefunction

In organic semiconductors, optical excitation does not necessarily produce free carriers. Very often, electron and hole are bound together to form an exciton. Releasing free carriers from the exciton is essential for the functioning of photovoltaics and optoelectronic devices, but it is a bottleneck process because of the high exciton binding energy. Inefficient exciton dissociation can limit the efficiency of organic photovoltaics. Here, nanoscale features that can allow the free carrier generation to occur spontaneously despite being an energy uphill process are determined. Specifically, by comparing the dissociation dynamics of the charge transfer (CT) exciton at two donor–acceptor interfaces, it is found that the relative orientation of the electron and hole wavefunction within a CT exciton plays an important role in determining whether the CT exciton will decompose into the higher energy free electron–hole pair or relax to the lower energy tightly‐bound CT exciton. The concept of the entropic driving force is combined with the structural anisotropy of typical organic crystals to devise a framework that can describe how the orientation of the delocalized electronic wavefunction can be manipulated to favor the energy‐uphill spontaneous dissociation of CT excitons over the energy‐downhill CT exciton cooling.     

Counterion Effect on the Energy Gap in Doped trans-Poly-acetylene (t-PA)

Doped t-PA is a well known benchmark model for studying the effect of a variety of atomic impurities on the energy gap variations in organic solids. This system is used here to study the effect of cationic and anionic impurities on the energy gap, leading to the observed phase transitions from insulator to metallic conductor behaviour displayed by this system. The model used is based on a cluster-like approach to the doped t-PA system, and the analysis is performed by focusing on the electrostatic and non-electrostatic contributions to the energy gap variations upon doping with different Lewis acids and bases at both low and high charge transfer regimes. The variations of the energy gap naturally appear to be associated with the fluctuation of the electrostatic potential induced by the host–:guest charge transfer.     

The role of structural reorganization in charge carrier transfer in a DNA molecule

The model proposed for hole transfer in DNA molecules with different configurations allows for the changes in the reorganization energy during charge transfer in a nucleotide strand with variations in the degree of orbital overlap in neighboring nucleotide pairs in different molecular sequences. The rate of hole transfer occurring in a DNA molecule through the superexchange and hopping transfer mechanisms is limited by the vibrational relaxation of the geometry of the nucleotide bases, as well as by the dynamics of solvent molecules. The rate of charge transfer in the DNA molecule depends on the height of the potential barrier between the donor fragment and the molecular bridge and on the positional arrangement of nucleobase pairs and their number in the molecular bridge. Inclusion of the interstrand charge transfer, which is characterized by a small degree of orbital overlap in the nucleobases of the opposite strands, does not affect the total charge transfer in the DNA molecule. An increase of the number of parallel components (processes) in the hopping mechanism entails an increase in the rate of charge transfer in the double helix.     

Voltage Losses in Organic Solar Cells: Understanding the Contributions of Intramolecular Vibrations to Nonradiative Recombinations

The large voltage losses usually encountered in organic solar cells significantly limit the power conversion efficiencies (PCEs) of these devices, with the result that the current highest PCE values in single‐junction organic photovoltaic remain smaller than for other solar cell technologies, such as crystalline silicon or perovskite solar cells. In particular, the nonradiative recombinations to the electronic ground state from the lowest‐energy charge‐transfer (CT) states at the donor–acceptor interfaces in the active layer of organic devices, are responsible for a significant part of the voltage losses. Here, to better comprehend the nonradiative voltage loss mechanisms, a fully quantum‐mechanical rate formula is employed within the framework of time‐dependent perturbation theory, combined with density functional theory. The objective is to uncover the specific contributions of intramolecular vibrations to the CT‐state nonradiative recombinations in several model systems, which include small‐molecule and polymer donors as well as fullerene and nonfullerene acceptors.