In this Letter, we study the role of the donor:acceptor interface nanostructure upon charge separation and recombination in organic photovoltaic devices and blend films, using mixtures of PBTTT and two different fullerene derivatives (PC70BM and ICTA) as models for intercalated and nonintercalated morphologies, respectively. Thermodynamic simulations show that while the completely intercalated system exhibits a large free-energy barrier for charge separation, this barrier is significantly lower in the nonintercalated system and almost vanishes when energetic disorder is included in the model. Despite these differences, both femtosecond-resolved transient absorption spectroscopy (TAS) and time-delayed collection field (TDCF) exhibit extensive first-order losses in both systems, suggesting that geminate pairs are the primary product of photoexcitation. In contrast, the system that comprises a combination of fully intercalated polymer:fullerene areas and fullerene-aggregated domains (1:4 PBTTT:PC70BM) is the only one that shows slow, second-order recombination of free charges, resulting in devices with an overall higher short-circuit current and fill factor. This study therefore provides a novel consideration of the role of the interfacial nanostructure and the nature of bound charges and their impact upon charge generation and recombination.
The power conversion efficiency (PCE) of state-of-the-art organic solar cells is still limited by significant open-circuit voltage (V-OC) losses, partly due to the excitonic nature of organic materials and partly due to ill-designed architectures. Thus, quantifying different contributions of the V-OC losses is of importance to enable further improvements in the performance of organic solar cells. Herein, the spectroscopic and semiconductor device physics approaches are combined to identify and quantify losses from surface recombination and bulk recombination. Several state-of-the-art systems that demonstrate different V-OC losses in their performance are presented. By evaluating the quasi-Fermi level splitting (QFLS) and the V-OC as a function of the excitation fluence in nonfullerene-based PM6:Y6, PM6:Y11, and fullerene-based PPDT2FBT:PCBM devices with different architectures, the voltage losses due to different recombination processes occurring in the active layers, the transport layers, and at the interfaces are assessed. It is found that surface recombination at interfaces in the studied solar cells is negligible, and thus, suppressing the non-radiative recombination in the active layers is the key factor to enhance the PCE of these devices. This study provides a universal tool to explain and further improve the performance of recently demonstrated high-open-circuit-voltage organic solar cells.
Power conversion efficiencies of donor/acceptor organic solar cells utilizing nonfullerene acceptors have now increased beyond the record of their fullerene-based counterparts. There remain many fundamental questions regarding nanomorphology, interfacial states, charge generation and extraction, and losses in these systems. Herein, we present a comparative study of bulk heterojunction solar cells composed of a recently introduced naphthothiadiazole-based polymer (NT812) as the electron donor and two different acceptor molecules, namely, [6,6]-phenyl-C71-butyric acid methyl ester (PCBM)[70] and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (ITIC). A comparison between the photovoltaic performance of these two types of solar cells reveals that the open-circuit voltage (Voc) of the NT812:ITIC-based solar cell is larger, but the fill factor (FF) is lower than that of the NT812:PCBM[70] device. We find the key reason behind this reduced FF in the ITIC-based device to be faster nongeminate recombination relative to the NT812:PCBM[70] system.
Organic solar cells have the potential to become the cheapest form of electricity. Rapid increase in the power conversion efficiency of organic solar cells (OSCs) has been achieved with the development of non-fullerene small-molecule acceptors. Next generation photovoltaics based upon environmentally benign "green solvent" processing of organic semiconductors promise a step-change in the adaptability and versatility of solar technologies and promote sustainable development. However, high-performing OSCs are still processed by halogenated (non-environmentally friendly) solvents, so hindering their large-scale manufacture. In this perspective, we discuss the recent progress in developing highly efficient OSCs processed from eco-compatible solvents, and highlight research challenges that should be addressed for the future development of high power conversion efficiencies devices.
State-of-the-art organic solar cells exhibit power conversion efficiencies of 18% and above. These devices benefit from the suppression of free charge recombination with regard to the Langevin limit of charge encounter in a homogeneous medium. It is recognized that the main cause of suppressed free charge recombination is the reformation and resplitting of charge-transfer (CT) states at the interface between donor and acceptor domains. Here, we use kinetic Monte Carlo simulations to understand the interplay between free charge motion and recombination in an energetically disordered phase-separated donor-acceptor blend. We identify conditions for encounter-dominated and resplitting-dominated recombination. In the former regime, recombination is proportional to mobility for all parameters tested and only slightly reduced with respect to the Langevin limit. In contrast, mobility is not the decisive parameter that determines the nongeminate recombination coefficient, k(2), in the latter case, where k2 is a sole function of the morphology, CT and charge-separated (CS) energetics, and CT-state decay properties. Our simulations also show that free charge encounter in the phase-separated disordered blend is determined by the average mobility of all carriers, while CT reformation and resplitting involves mostly states near the transport energy. Therefore, charge encounter is more affected by increased disorder than the resplitting of the CT state. As a consequence, for a given mobility, larger energetic disorder, in combination with a higher hopping rate, is preferred. These findings have implications for the understanding of suppressed recombination in solar cells with nonfullerene acceptors, which are known to exhibit lower energetic disorder than that of fullerenes.
Understanding and disentangling photophysical properties of long-lived photoexcitations in bulk heterojunction (BHJ) solar cells, which contribute mostly to photocurrent, provide essential guidelines to their improvement. However, to construct improved physical models, their rational design relies on reliable measurement techniques for charge recombination. Here, we combine photocurrent and photoinduced absorption spectroscopy (PCPIA) to directly probe the free carrier concentration and investigate loss mechanisms of long-lived excitations in nearly 10% efficient PPDT2FBT/PC70BM BHJ solar cells under steady-state operational conditions. From the PCPIA data obtained under open- circuit and short-circuit conditions, the absorption cross section and the concentration of photoexcitations are obtained. This material system exhibits an exceptionally low bimolecular recombination rate, about 300 times smaller than the diffusion-controlled electron and hole encounter rate. Furthermore, we observe that the fill factor is limited by losses originating from long-lived photoexcitations undergoing dispersive bimolecular recombination.
While the performance of laboratory-scale organic solar cells (OSCs) continues to grow, development of high efficiency large area OSCs remains a big challenge. Although a few attempts to produce large area organic solar cells (OSCs) have been reported, there are still challenges on the way to realizing efficient module devices, such as the low compatibility of the thickness-sensitive active layer with large area coating techniques, the frequent need for toxic solvents and tedious optimization processes used during device fabrication. In this work, highly efficient thickness-insensitive OSCs based on PTB7-Th:PC71BM that processed with single-component green solvent 2-methylanisole are presented, in which both junction thickness limitation and solvent toxicity issues are simultaneously addressed. Careful investigation reveals that this green solvent prevents the evolution of PC71BM into large area clusters resulting in reduced charge carrier recombination, and largely eliminates trapping centers, and thus improves the thickness tolerance of the films. These findings enable us to address the scalability and solvent toxicity issues and to fabricate a 16 cm(2) OSC with doctor-blade coating with a state-of-the-art power conversion efficiency of 7.5% using green solvent.
A Shockley-Type polymer
(2018)
Charge extraction rate in solar cells made of blends of electron donating/accepting organic semiconductors is typically slow due to their low charge carrier mobility. This sets a limit on the active layer thickness and has hindered the industrialization of organic solar cells (OSCs). Herein, charge transport and recombination properties of an efficient polymer (NT812):fullerene blend are investigated. This system delivers power conversion efficiency of >9% even when the junction thickness is as large as 800 nm. Experimental results indicate that this material system exhibits exceptionally low bimolecular recombination constant, 800 times smaller than the diffusion-controlled electron and hole encounter rate. Comparing theoretical results based on a recently introduced modified Shockley model for fill factor, and experiments, clarifies that charge collection is nearly ideal in these solar cells even when the thickness is several hundreds of nanometer. This is the first realization of high-efficiency Shockley-type organic solar cells with junction thicknesses suitable for scaling up.
Despite the myriad of organic donor:acceptor materials, only few systems have emerged in the life of organic solar cells to, exhibit considerable reduced bimolecular recombination, with respect to the random encounter rate given by the Langevin equation. Monte Carlo simulations have revealed that the rate constant of the formation of electron-hole bound states depends on the random encounter of opposite charges and is nearly given by the Langevin equation for the domain sizes relevant to efficient bulk heterojunction systems. Recently, three studies :suggested that charge transfer states dissociating much faster than their decay rate to the ground state, can result in reduced bimolecular recombination by lowering the recombination rate to the ground state as a loss pathway. A separate study identified another loss pathway and suggested that forbidden back electron transfer from triplet charge transfer states to triplet excitons is a key to achieving reduced recombination. Herein we further explain the reduced bimolecular recombination by investigating the limitations of these two proposals. By solving kinetic rate equations for a BHJ system with realistic rates, we show that both of these previously presented conditions must only be held at the same time fora system to exhibit non-Langevin behavior. We demonstrate that suppression of both of the parallel loss channels of singlet and triplet states can be achieved through increasing the dissociation rate of the charge transfer states; a crucial requirement to achieve a high charge carrier extraction efficiency.
The increase in the performance of organic solar cells observed over the past few years has reinvigorated the search for a deeper understanding of the loss and extraction processes in this class of device. A detailed knowledge of the density of free charge carriers under different operating conditions and illumination intensities is a prerequisite to quantify the recombination and extraction dynamics. Differential charging techniques are a promising approach to experimentally obtain the charge carrier density under the aforementioned conditions. In particular, the combination of transient photovoltage and photocurrent as well as impedance and capacitance spectroscopy have been successfully used in past studies to determine the charge carrier density of organic solar cells. In this Tutorial, these experimental techniques will be discussed in detail, highlighting fundamental principles, practical considerations, necessary corrections, advantages, drawbacks, and ultimately their limitations. Relevant references introducing more advanced concepts will be provided as well. Therefore, the present Tutorial might act as an introduction and guideline aimed at new prospective users of these techniques as well as a point of reference for more experienced researchers. Published under an exclusive license by AIP Publishing.