Charge Transfer State Dissociation Research Articles

An Impedance Study of the Density of States Distribution in Blends of PM6:Y6 in Relation to Barrierless Dissociation of CT States

AbstractIn an endeavor to understand why the dissociation of charge‐transfer (CT) states in a PM6:Y6 solar‐cell is not a thermally activated process, measurements of energy‐resolved impedance as well as of intrinsic photoconduction are employed. This study determines the density of states distributions of the pertinent HOMO and LUMO states and obtains a Coulomb binding energy (Eb,CT) of ≈150 meV. This is 250 meV lower than the value expected for a pair of localized charges with 1 nm separation. The reason is that the hole is delocalized in the polymer and the electron is shared among Y6 molecules forming a J‐like aggregate. There are two key reasons why this binding energy of the CT state is not reflected in the temperature dependence of the photocurrent of PM6:Y6‐diode: i) The e–h dissociation in a disordered system is a multi‐step process whose activation energy is principally different from the binding energy of the CT state and can be substantially less than Eb,CT, and ii) since dissociation of the CT state competes with its intrinsic decay, the dissociation yield saturates once the rate of dissociation grossly exceeds the rate of intrinsic decay. This study argues that these conditions are met in a PM6:Y6‐solar cell.

Charge generation in organic solar cells: Journey toward 20% power conversion efficiency

AbstractThe power conversion efficiencies of organic solar cells (OSCs) have routinely lagged far behind those of their inorganic counterparts. However, owing to the enormous contributions of many researchers, the power conversion efficiencies of OSCs have rapidly improved and now exceed 19%. The charge generation mechanisms in OSCs have been heavily debated during this period while acquiring valuable knowledge. This review highlights fundamental and cutting‐edge research that rationalizes why OSCs can generate photocurrent so efficiently. In particular, a photophysicist's views on exciton diffusion to donor:acceptor interfaces, charge transfer at the donor:acceptor interface, and long‐range spatial dissociation of charge transfer states are discussed. Although a general consensus in this area has not been reached yet, recent time‐resolved spectroscopic measurements provide important photophysical insights that can help achieving a better understanding of the charge generation mechanism in OSCs. Based on these observations, future research directions for realizing further improvements in OSC performance are discussed.

Delocalization suppresses nonradiative charge recombination in polymer solar cells

Suppressing nonradiative deactivation of charge transfer (CT) states is pivotal to realizing further improvements in the power conversion efficiencies of polymer solar cells (PSCs). According to the energy gap law, the nonradiative decay rate constant knr scales exponentially with decreasing CT state energy ECT; thereby, as long as knr is governed by the energy gap law, a decrease in ECT will inevitably increase nonradiative deactivation of CT states and hence decrease the power conversion efficiency. Here, we report the nonradiative decay dynamics of CT states generated in various nonfullerene-acceptor-based PSCs by using transient absorption spectroscopy. The absence of a strong correlation between knr and ECT indicates that the energy gap law is not valid for these PSCs and that parameters other than ECT contribute significantly to knr. We found that knr decreased with an increase in materials’ crystallinities, indicating that increasing crystallinity leads to CT state delocalization, which in turn mitigates the nonradiative deactivation of CT states. We report the nonradiative decay dynamics of charge transfer (CT) states generated in nonfullerene-acceptor-based polymer solar cells. The nonradiative decay rate constants knr decreased with an increase in the efficiency for dissociation of CT states into free carriers, indicating that nonradiative decay of CT states can be mitigated by increasing the delocalization of the CT state wave function.

Correlation between molecular configuration and charge transfer dynamics in highly efficient organic solar cells

Molecular design and charge transport dynamics play an important role in achieving highly efficient organic solar cells (OSCs). In this work, non-fullerene acceptor Y6, its alkyl chain modified derivative N3 and halogen-replaced derivative BTP-BO-4Cl are selected to fabricate OSCs. The OSCs obtain a high power conversion efficiency (PCE) of 16.86%. The impact of different modification methods on molecular configuration and energy level matching is investigated systematically by time-resolved photoluminescence (TRPL) and transient absorption spectroscopy (TAS). The results demonstrate that side chain modification has a positive effect on molecular layer spacing, domain area size and charge carrier mobilities. More importantly, halogen atom replacing has the similar but more positive impact, bringing a higher PCE than side chain modification. The overall processes of charge generation, dissociation and recombination in OSCs are studied systematically for the first time. For the best-performance device, the lifetimes of singlet exciton recombination (τ1), charge transfer (CT) state recombination (τ2), singlet exciton dissociation (τ3) and CT state dissociation (τ4) are calculated as ∼500 ps, ∼2 ns, ∼200 fs and ∼1 ps, respectively. The correlation between molecular configuration and charge transfer dynamics is established, which can provide a guideline for designing materials of highly efficient OSCs.

Intrachain Delocalization Effect of Charge Carriers on the Charge-Transfer State Dynamics in Organic Solar Cells

We studied the charge-generation mechanism in low-bandgap polymer (P4TNTz-2F)-fullerene bulk heterojunction (BHJ) organic solar cells (OSCs) using transient absorption (TA) spectroscopy. The highly crystalline nanowire structure of P4TNTz-2F in a blend film prepared with chlorobenzene (CB) and 1,8-diiodooctane (DIO) induced more long-lived charge carriers than those in a blend film prepared with CB only. Pump-wavelength-dependent TA data revealed that the increased charge-delocalization by the intrachain ordering of P4TNTz-2F in the blend film prepared with CB/DIO is the key factor to increasing the OSC efficiency. The intrachain charge-delocalization increased the charge-transfer (CT) state lifetime and suppressed geminate recombination losses, resulting in the efficient dissociation of CT states into free carriers. Our findings provide new insights into the excited-state dynamics study of BHJ blends, which can serve as a good guide for the development of novel OSC materials.

Charge Photogeneration in Non‐Fullerene Organic Solar Cells: Influence of Excess Energy and Electrostatic Interactions

AbstractIn organic solar cells, photogenerated singlet excitons form charge transfer (CT) complexes, which subsequently split into free charge carriers. Here, the contributions of excess energy and molecular quadrupole moments to the charge separation process are considered. The charge photogeneration in two separate bulk heterojunction systems consisting of the polymer donor PTB7‐Th and two non‐fullerene acceptors, ITIC and h‐ITIC, is investigated. CT state dissociation in these donor–acceptor systems is monitored by charge density decay dynamics obtained from transient absorption experiments. The electric field dependence of charge carrier generation is studied at different excitation energies by time delayed collection field (TDCF) and sensitive steady‐state photocurrent measurements. Upon excitation below the optical gap, free charge carrier generation becomes less field dependent with increasing photon energy, which challenges the view of charge photogeneration proceeding through energetically lowest CT states. The average distance between electron–hole pairs at the donor–acceptor interface is determined from empirical fits to the TDCF data. The delocalization of CT states is larger in PTB7‐Th:ITIC, the system with larger molecular quadrupole moment, indicating the sizeable effect of the electrostatic potential at the donor–acceptor interface on the dissociation of CT complexes.

Exciton and Charge Carrier Dynamics in Highly Crystalline PTQ10:IDIC Organic Solar Cells

AbstractHerein the morphology and exciton/charge carrier dynamics in bulk heterojunctions (BHJs) of the donor polymer PTQ10 and molecular acceptor IDIC are investigated. PTQ10:IDIC BHJs are shown to be particularly promising for low cost organic solar cells (OSCs). It is found that both PTQ10 and IDIC show remarkably high crystallinity in optimized BHJs, with GIWAXS data indicating pi‐pi stacking coherence lengths of up to 8 nm. Exciton‐exciton annihilation studies indicate long exciton diffusion lengths for both neat materials (19 nm for PTQ10 and 9.5 nm for IDIC), enabling efficient exciton separation with half lives of 1 and 3 ps, despite the high degree of phase segregation in this blend. Transient absorption data indicate exciton separation leads to the formation of two spectrally distinct species, assigned to interfacial charge transfer (CT) states and separated charges. CT state decay is correlated with the appearance of additional separate charges, indicating relatively efficient CT state dissociation, attributed to the high crystallinity of this blend. The results emphasize the potential for high material crystallinity to enhance charge separation and collection in OSCs, but also that long exciton diffusion lengths are likely to be essential for efficient exciton separation in such high crystallinity devices.

Spectroscopic Investigation of the Effect of Microstructure and Energetic Offset on the Nature of Interfacial Charge Transfer States in Polymer: Fullerene Blends.

Despite performance improvements of organic photovoltaics, the mechanism of photoinduced electron–hole separation at organic donor–acceptor interfaces remains poorly understood. Inconclusive experimental and theoretical results have produced contradictory models for electron–hole separation in which the role of interfacial charge-transfer (CT) states is unclear, with one model identifying them as limiting separation and another as readily dissociating. Here, polymer–fullerene blends with contrasting photocurrent properties and enthalpic offsets driving separation were studied. By modifying composition, film structures were varied from consisting of molecularly mixed polymer–fullerene domains to consisting of both molecularly mixed and fullerene domains. Transient absorption spectroscopy revealed that CT state dissociation generating separated electron–hole pairs is only efficient in the high energy offset blend with fullerene domains. In all other blends (with low offset or predominantly molecularly mixed domains), nanosecond geminate electron–hole recombination is observed revealing the importance of spatially localized electron–hole pairs (bound CT states) in the electron–hole dynamics. A two-dimensional lattice exciton model was used to simulate the excited state spectrum of a model system as a function of microstructure and energy offset. The results could reproduce the main features of experimental electroluminescence spectra indicating that electron–hole pairs become less bound and more spatially separated upon increasing energy offset and fullerene domain density. Differences between electroluminescence and photoluminescence spectra could be explained by CT photoluminescence being dominated by more-bound states, reflecting geminate recombination processes, while CT electroluminescence preferentially probes less-bound CT states that escape geminate recombination. These results suggest that apparently contradictory studies on electron–hole separation can be explained by the presence of both bound and unbound CT states in the same film, as a result of a range of interface structures.

Effects of additive-solvents on the mobility and recombination of a solar cell based on PTB7-Th:PC71BM

We have performed a study on the effect of the 1,8-diiodooctane (DIO) additive on the performance of an organic bulk-heterojunction solar cell made with PTB7-Th:PC71BM nanostructured blend. The devices were fabricated using either pure chlorobenzene as solvent or mixed with 1,8-diiodooctane. Current-voltage measurements carried in dark, at different temperatures, were analyzed by the Mott-Gurney equation, in which the charge carrier mobility was obtained as fitting parameter. On the sequence, current-voltage curves recorded under 1 Sun illumination, also at different temperatures, were fitted by an analytical equation for the photocurrent, which took into account second-order kinetics for the bimolecular recombination. It is already known that DIO additive selectively dissolves the fullerene and reduces the domain sizes of PC71BM forming a donor-acceptor bicontinuous interpenetrating network, resulting in an increase of the device external quantum efficiency. From the adjustments obtained by the measurements in dark, and that of the photocurrent equation on the photovoltaic responses, we analyzed the effect of temperature on the charge carrier mobility µ and on the recombination reduction factor ζ. It was evident that the effect of DIO on the morphology of the active layer improves the conduction process by hopping, and decreases the recombination coefficient. This improvement of the photocurrent response is most probably due to the fragmentation of the PC71BM aggregates and their better permeation in the polymer matrix of PTB7-Th, which facilitates the dissociation of charge transfer states at PTB7-Th:PC71BM interfaces.

The Role of Mobility on Charge Generation, Recombination, and Extraction in Polymer‐Based Solar Cells

AbstractOrganic semiconductors are of great interest for a broad range of optoelectronic applications due to their solution processability, chemical tunability, highly scalable fabrication, and mechanical flexibility. In contrast to traditional inorganic semiconductors, organic semiconductors are intrinsically disordered systems and therefore exhibit much lower charge carrier mobilities—the Achilles heel of organic photovoltaic cells. In this progress review, the authors discuss recent important developments on the impact of charge carrier mobility on the charge transfer state dissociation, and the interplay of free charge extraction and recombination. By comparing the mobilities on different timescales obtained by different techniques, the authors highlight the dispersive nature of these materials and how this reflects on the key processes defining the efficiency of organic photovoltaics.

Decoupling Photocurrent Loss Mechanisms in Photovoltaic Cells Using Complementary Measurements of Exciton Diffusion

AbstractSignificant work has been directed at measuring the exciton diffusion length (LD) in organic semiconductors due to its significance in determining the performance of photovoltaic cells. Several techniques have been developed to measure LD, often probing photoluminescence or charge carrier generation. Interestingly, in this study it is shown that when different techniques are compared, both the diffusive behavior of the exciton and active carrier recombination loss pathways can be decoupled. Here, a planar heterojunction device based on the donor–acceptor pairing of boron subphthalocyanine chloride‐C60 is examined using photoluminescence quenching, photovoltage‐, and photocurrent‐based LD measurement techniques. Photovoltage yields the device relevant LD of both active materials as a function of forward bias subject to geminate recombination losses. These values are used to accurately predict the photocurrent as a function of voltage, suggesting geminate recombination is the dominant mechanism responsible for photocurrent loss. By combining these measurements with photocurrent and photoluminescence quenching, the intrinsic LD, as well as the voltage‐dependent charge transfer state dissociation and charge collection efficiencies are quantitatively determined. The results of this work provide a method to decouple all relevant loss pathways during photoconversion, and establish the factors that can limit the performance of excitonic photovoltaic cells.

Dissociation of charge-transfer states at donor–acceptor interfaces of organic heterojunctions

The dissociation of charge-transfer (CT) states into free charge carriers at donor–acceptor (DA) interfaces is an important step in the operation of organic solar cells and related devices. In this paper, we show that the effect of DA morphology and architecture means that the directions of CT states (where a CT state’s direction is defined as the direction from the electron to the hole of the CT state) may deviate from the direction of the applied electric field. The deviation means that the electric field is not fully utilized to assist, and could even hinder the dissociation process. Furthermore, we show that the correct charge carrier mobilities that should be used to describe CT state dissociation are the actual mobilites at DA interfaces. The actual mobilities are defined in this paper, and in general are not the same as the mobilities that are used to calculate electric currents which are the mobilites along the direction of the electric field. Then, to correctly describe CT state dissociation, we modify the widely used Onsager–Braun (OB) model by including the effect of DA morphology and architecture, and by employing the correct mobilities. We verify that when the modified OB model is used to describe CT state dissociation, the fundamental issues that concern the original OB model are resolved. This study demonstrates that DA morphology and architecture play an important role by strongly influencing the CT state dissociation as well as the mobilites along the direction of the electric field.

Extended Intermolecular Interactions Governing Photocurrent-Voltage Relations in Ternary Organic Solar Cells.

Efficient organic solar cells are based on (electron) donor-acceptor heterojunctions. An optically generated excited molecular state (exciton) is dissociated at this junction, forming a charge-transfer (CT) state in an intermediate step before the electron and hole are completely separated. The observed highly efficient dissociation of this Coulombically bound state raises the question on the dissociation mechanism. Here, we show that the observed high quantum yields of charge carrier generation and CT state dissociation are due to extended (and consequently weakly bound) CT states visible in absorption and emission spectra and first-principles calculations. Identifying a new geminate-pair loss mechanism via donor excimers, we find that the hole on the small-molecule donor is not localized on a single molecule and charge separation is correlated with the energetic offset between excimer and CT states. Thus, the charges upon interface charge transfer and even in the case of back-transfer and recombination are less localized than commonly assumed.

Theoretical Study of the Charge-Transfer State Separation within Marcus Theory: The C60-Anthracene Case Study

We study, within Marcus theory, the possibility of the charge-transfer (CT) state splitting at organic interfaces and a subsequent transport of the free charge carriers to the electrodes. As a case study we analyze model anthracene-C60 interfaces. Kinetic Monte Carlo (KMC) simulations on the cold CT state were performed at a range of applied electric fields, and with the fields applied at a range of angles to the interface to simulate the action of the electric field in a bulk heterojunction (BHJ) interface. The results show that the inclusion of polarization in our model increases CT state dissociation and charge collection. The effect of the electric field on CT state splitting and free charge carrier conduction is analyzed in detail with and without polarization. Also, depending on the relative orientation of the anthracene and C60 molecules at the interface, CT state splitting shows different behavior with respect to both applied field strength and applied field angle. The importance of the hot CT in helping the charge carrier dissociation is also analyzed in our scheme.

A Combined Theoretical and Experimental Study of Dissociation of Charge Transfer States at the Donor-Acceptor Interface of Organic Solar Cells.

The observation that in efficient organic solar cells almost all electron-hole pairs generated at the donor-acceptor interface escape from their mutual coulomb potential remains to be a conceptual challenge. It has been argued that it is the excess energy dissipated in the course of electron or hole transfer at the interface that assists this escape process. The current work demonstrates that this concept is unnecessary to explain the field dependence of electron-hole dissociation. It is based upon the formalism developed by Arkhipov and co-workers as well as Baranovskii and co-workers. The key idea is that the binding energy of the dissociating "cold" charge-transfer state is reduced by delocalization of the hole along the polymer chain, quantified in terms of an "effective mass", as well as the fractional strength of dipoles existent at the interface in the dark. By covering a broad parameter space, we determine the conditions for efficient electron-hole dissociation. Spectroscopy of the charge-transfer state on bilayer solar cells as well as measurements of the field dependence of the dissociation yield over a broad temperature range support the theoretical predictions.

Dissociation of Charge Transfer States and Carrier Separation in Bilayer Organic Solar Cells: A Time-Resolved Electroabsorption Spectroscopy Study.

Ultrafast optical probing of the electric field by means of Stark effect in planar heterojunction cyanine dye/fullerene organic solar cells enables one to directly monitor the dynamics of free electron formation during the dissociation of interfacial charge transfer (CT) states. Motions of electrons and holes is scrutinized separately by selectively probing the Stark shift dynamics at selected wavelengths. It is shown that only charge pairs with an effective electron-hole separation distance of less than 4 nm are created during the dissociation of Frenkel excitons. Dissociation of the coulombically bound charge pairs is identified as the major rate-limiting step for charge carriers' generation. Interfacial CT states split into free charges on the time-scale of tens to hundreds of picoseconds, mainly by electron escape from the Coulomb potential over a barrier that is lowered by the electric field. The motion of holes in the small molecule donor material during the charge separation time is found to be insignificant.

High Electron Mobility and Its Role in Charge Carrier Generation in Merocyanine/Fullerene Blends

Charge carrier generation and drift dynamics have been investigated in two types of dye:fullerene heterojunctions: vacuum-deposited merocyanine:C60 and solution-processed merocyanine:PC61BM blends by combining electric-field-induced fluorescence quenching and ultrafast time-resolved carrier drift measurements. We demonstrate that interfacial charge transfer (CT) states are strongly heterogeneous with energies dependent on the acceptor material and its domain sizes. Interfacial CT states on large C60 domains have low energies, while CT states on PC61BM domains have larger energies, which are weakly dependent on the domain sizes. We distinguish two interfacial CT state dissociation pathways: (i) ultrafast, weakly dependent on the electric field and (ii) slow field-assisted dissociation during entire CT state lifetime. We attribute process i to low-energy, weakly bound CT states on large fullerene domains and process ii to strongly bound CT states on small domains or single fullerene molecules. The electron mobility in films with 50% of C60 is several times higher than in the films with PC61BM and orders of magnitude higher than the hole mobility. We conclude that efficient carrier generation at low electric fields typical for operating solar cells relies on unperturbed motion of highly mobile electrons; thus, fast motion and extraction of electrons are crucial for efficient solar cells.

Photogeneration and recombination of charge carrier pairs and free charge carriers in polymer/fullerene bulk heterojunction films

AbstractPhoto‐generation and recombination of free charge carriers in poly‐3 (hexylthiophene) (P3HT) and [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) blend films has been studied at different PCBM concentrations by means of fluorescence spectroscopy and transient photocurrent methods. We show that more than 80% of excitons form charge transfer (CT) states at PCBM concentrations above 4%. Efficiency of the CT state dissociation into free charge carries strongly depends on the PCBM concentration; the dissociation efficiency increases more than 30 times when PCBM concentration increases from 1 to 32%. We attribute the strong concentration dependence to formation of PCBM clusters facilitating electron migration and/or delocalization. Reduced charge carrier recombination coefficient has also been observed at high PCBM concentrations. We suggest that this may be partly caused by the reduced stability of reformed Coulombicaly bound charge pairs.

Vibrational Energy Mediates Charge Separation in Organic Photovoltaic Materials

Charge separation and charge trapping following photoinduced electron transfer from the conjugated polymer, poly (2-methoxy-5-ethylhexyloxy-1,4-phenylenecyanovinylene (CN-MEH-PPV), to the electron accepting functionalized fullerene, [6,6]-phenyl C61-butyric acid methyl ester (PCBM), is directly measured using ultrafast vibrational spectroscopy. Our group previously demonstrated that the vibrational frequency of the carbonyl (C=O) stretch of PCBM is sensitive to the location of the molecules relative to the interfaces formed between PCBM clusters and CN-MEH-PPV. The correlation between the carbonyl frequency and the proximity of PCBM molecules to the interfaces enables the time evolution of the frequency of the bleach peak to be interpreted in terms of dissociation of charge transfer states into charge separated states. Temperature-dependent measurements of the rate of this charge separation process indicate that excess vibrational energy in “hot” charge transfer states resulting from the electron transfer reaction enables electrons to escape their Coulombic potentials at the interfaces on ultrafast timescales. Furthermore, temperature-dependent measurements on longer timescales indicate that after the initial charge separation reaction, electrons enter shallow trap states that, on the basis of the radial variation of vibrational frequencies, lie in the interior of PCBM clusters. The vibrational spectra suggest that these interior regions have higher intermolecular order in comparison to the interfaces.

Nonideal parasitic resistance effects in bulk heterojunction organic solar cells

A common assumption in both experimental measurements and device modeling of bulk heterojunction (BHJ) organic solar cells is that parasitic resistances are ideal. In other words, series resistance (Rsr) is near zero while shunt resistance (Rsh) approaches infinity. Relaxation of this assumption affects device performance differently depending on the chosen BHJ material system. Specifically, the impact of nonideal Rsr is controlled by the electric field dependence of the probability of charge transfer (CT) state dissociation (PCT). This is demonstrated by evaluating the experimental current density versus voltage response within the framework of a drift/diffusion model for two BHJ systems that strongly differ in PCT. Second, light intensity measurements of devices with nonideal Rsr and Rsh are shown to convolute the scaling of short-circuit current and open-circuit voltage with light intensity, which is a common technique to study BHJ device physics. Finally, we show the connection between the drift/diffusion and equivalent circuit model with regard to each model’s treatment of CT state dissociation. In particular, the equivalent circuit model utilizes a light intensity dependent Rsh to describe this dissociation process and predicts a photocurrent under reverse bias that exceeds the photocurrent permitted by light absorption.