Bimolecular Charge Recombination Research Articles

Correlating the Photovoltaic Performance and Stability of the All-Small-Molecule Organic Solar Cells to Their Intermixed Phases Determined by Concentration-Dependent Ultraviolet-Visible Absorption Spectroscopy.

In addition to the donor-acceptor nano phases, the intermixed phase within the organic blends is crucial for the photovoltaic performance and stability of the bulk-heterojunction organic solar cells (OSCs). Here, the intermixed phase of a representative M-PhS:BTP-eC9 all-small-molecule organic solar cell was investigated by a concentration-dependent ultraviolet-visible (UV-vis) absorption spectroscopy method, where a shift of the absorption maximum wavelength was measured for the acceptor component with the increase of the acceptor concentration. The blend ratios of the acceptor to the donor in the intermixed phase, corresponding to the critical concentration for the formation of the acceptor nanophase (CAP), were determined to be 0.35, 0.20, and 0.15 for the as-cast, thermal annealing (TA), and the combined TA and solvent vapor annealing films. These results indicated that M-PhS and BTP-eC9 are kinetically well intermixed during spin coating, whereas TA and the following solvent annealing promote the crystallization of BTP-eC9 molecules out of the intermixed phase. The photovoltaic performance of the M-PhS:BTP-eC9 cells with different blend ratios was investigated. The formation of the BTP-eC9 nano phase in the blend film leads to stable VOC and fast increased JSC, which can be understood by the reduction of bimolecular charge recombination and the formation of electron transporting pathways within the photoactive layer. Similarly, the critical concentration for the formation of the donor phase was estimated to be 0.15 by measuring the stabilized VOC and increased JSC values of the cells with different donor blending ratios. More importantly, after a fast "burn-in" thermal degradation, the M-PhS:BTP-eC9 cell showed excellent thermal stability aging at 85 °C for over 1128 h, which is in good accordance with the unchanged intermixed phases measured by the UV-vis spectra of the annealed films. The current work demonstrates the feasibility of the spectroscopy method to investigate the intermixed phases for organic bulk-heterojunction solar cells and proves that all-small-molecule solar cells can be intrinsically very stable.

Impact of Intermolecular Interactions between Halogenated Volatile Solid Additives and the Nonfullerene Acceptor in Organic Solar Cells

AbstractThe halogenated volatile solid additives can delicately optimize the active layer morphology of organic solar cells, improving the devices' performance, stability, and reproducibility. However, what type of intermolecular interaction occurs between the solid additives and the active layer and whether the interaction truly impacts the donor or acceptor remains debatable. Herein, the focus is on halogenated volatile solid additives with conjugated benzene rings and their influence on the morphology of the active layer composed of PM6:Y6 as they evaporated. The absorbance spectra exhibit apparent red‐shift features in Y6 absorption regions, while the donor part is unaffected. The theoretical calculation results reveal that the additives can stay between two Y6 molecules and form halogen bonds, affecting the π–π aggregation properties of Y6. As a result, the crystalline features of the active layer are altered, leading to increased charge carrier mobilities, extended charge carrier diffusion lengths, reduced bimolecular charge recombination, and thus the device performance. Especially when 1,3,5‐tri bromobenzene is used, a champion power conversion efficiency of 17.9% is attained, among the best‐performed organic solar cells comprising PM6:Y6. The findings shed light on theoretical and experimental guidelines for designing and developing volatile solid additives for highly efficient nonfullerene organic solar cells.

Vertical Phase Regulation with 1,3,5-Tribromobenzene Leads to 18.5% Efficiency Binary Organic Solar Cells.

The sequential deposition method assists the vertical phase distribution in the photoactive layer of organic solar cells, enhancing power conversion efficiencies. With this film coating approach, the morphology of both layers can be fine-tuned with high boiling solvent additives, as frequently applied in one-step casting films. However, introducing liquid additives can compromise the morphological stability of the devices due to the solvent residuals. Herein, 1,3,5-tribromobenzene (TBB) with high volatility and low cost, is used as a solid additive in the acceptor solution and combined thermal annealing to regulate the vertical phase in organic solar cells composed of D18-Cl/L8-BO. Compared to the control cells, the devices treated with TBB and those that underwent additional thermal processing exhibit increased exciton generation rate, charge carrier mobility, charge carrier lifetime, and reduced bimolecular charge recombination. As a result, the TBB-treated organic solar cells achieve a champion power conversion efficiency of 18.5% (18.1% averaged), one of the highest efficiencies in binary organic solar cells with open circuit voltage exceeding 900mV. This study ascribes the advanced device performance to the gradient-distributed donor-acceptor concentrations in the vertical direction. The findings provide guidelines for optimizing the morphology of the sequentially deposited top layer to achieve high-performance organic solar cells.

Excited-State Dynamics in All-Polymer Blends with Polymerized Small-Molecule Acceptors.

Polymerizing small-molecular acceptors (SMAs) is a promising route to construct high performance polymer acceptors of all-polymer solar cells (all-PSCs). After SMA polymerization, the microstructure of molecular packing is largely modified, which is essential in regulating the excited-state dynamics during the photon-to-current conversion. Nevertheless, the relationship between the molecular packing and excited-state dynamics in polymerized SMAs (PSMAs) remains poorly understood. Herein, the excited-statedynamics and molecular packing are investigated in the corresponding PSMA and SMA utilizing a combination of experimental and theoretical methods. This study finds that the charge separation from intra-moiety delocalized states (i-DEs) is much faster in blends with PSMAs, but the loosed π-π molecular packing suppresses the excitation conversion from the local excitation (LE) to the i-DE, leading to additional radiative losses from LEs. Moreover, the increased aggregations of PSMA in the blends decrease donor: acceptor interfaces, which reduces triplet losses from the bimolecular charge recombination. These findings suggest that excited-state dynamics may be manipulated by the molecular packing in blends with PSMAs to further optimize the performance of all-PSCs.

Difluoro and dicyano substituted sexithiophene − isoindigo terpolymers enabling ternary polymer solar cells with a bulk heterojunction thickness 100 nm → 300 nm and a minor decline of efficiency 14.5 % → 14.0 %

In this work, difluoro and dicyano substituted terpolymers, P6TI-3N1F, P6TI-1N1F, and P6TI-1N3F, based on isoindigo − sexithiophene π-conjugated polymers have been designed and characterized. Together with two only cyano and only fluoro substituted copolymers, P6TIN and P6TIF, we have demonstrated that P6TI-1N1F is the champion terpolymer in terms of the ratio of electron/hole mobility, nanofibril and its agglomeration, monomolecular and bimolecular charge recombination, polymer chain face-on alignment, and photoluminescence quenching in a binary thin film of polymer:PC71BM or polymer:IT4F. In the binary polymer solar cells (PSCs) based on a bullk heterojunction (BHJ) of either polymer:PC71BM or polymer:IT4F, P6TI-1N1F exhibits the highest fill factor of 67.62 % or 76.86 %, and hence the highest power conversion efficiency (PCE) of 10.4 % or 11.9 %. Corresponding ternary PSCs with a 100 nm thick BHJ of P6TI-1N1F:IT4F:PC71BM or P6TI-1N1F:Y6:PC71BM exhibit PCE as high as 12.8 % or 14.5 %. It is rarely seen in literature that the PCE of the ternary PSCs shows only minor decline to 12.4 % or 14.0 % when the thickness of BHJ increases from 100 nm to 300 nm.

Suppressing Bimolecular Charge Recombination and Energetic Disorder with Planar Heterojunction Active Layer Enables 18.1% Efficiency Binary Organic Solar Cells

The performance of organic solar cells has been dramatically enhanced due to the use of bulk heterojunction active layer structure. However, blending donor and acceptor in the bulk volume results in a large extent of bimolecular charge recombination and increasing energetic disorder. Herein, we fabricated organic solar cells with polymer donor PM6 and nonfullerene acceptor N3 in bilayer structure to investigate the impact of planar heterojunction configurations on charge recombination and energetic landscapes. We find superior crystallinity features in the bilayer composed of pure donor and acceptor layers. The bimolecular charge recombination and energetic disorder are effectively suppressed compared with the bulk heterojunction counterparts. Thus, a power conversion efficiency as high as 18.1% (17.8% averaged) is achieved, which stands among the top values of planar heterojunction organic solar cells. In addition, improved device shelf stability is observed because of the fewer donor–acceptor interfaces in the active layer. Our results suggest that a planar heterojunction structure could efficiently suppress the bimolecular charge recombination and energetic disorder, providing an alternative pathway for developing solution-processed organic solar cells.

Charge Carrier Dynamics in Planar Heterojunction Organic Solar Cells

The ionization energy (IE) offset of a donor–acceptor pair provides the driving force for hole transfer and subsequent free charge carrier generation in low‐bandgap nonfullerene organic solar cells (OSCs). However, the interfacial energetic landscape in bulk heterojunction OSCs is determined by the materials’ electronic structure and intermolecular interactions at the donor/acceptor interface, causing local energy‐level shifts and disorder. Herein, the impact of the IE offset on the charge transfer efficiency and charge carrier dynamics is systematically evaluated by characterizing PM6/ITIC, PM6/IT‐2Cl, and PM6/IT‐4Cl planar heterojunction (PHJ) solar cells. Ultrafast spectroscopy and time‐resolved charge carrier density measurements reveal that an IE offset of about ≈0.5 eV leads to efficient hole transfer and subsequent free charge generation. Furthermore, bimolecular charge recombination and consequently triplet generation are significantly reduced in systems with high IE offset. This work underlines the importance of sizeable donor–acceptor IE offsets in PHJ nonfullerene OSCs as critical for high‐efficiency donor/acceptor material and device design.

Reduced bimolecular charge recombination in efficient organic solar cells comprising non-fullerene acceptors

Bimolecular charge recombination is one of the most important loss processes in organic solar cells. However, the bimolecular recombination rate in solar cells based on novel non-fullerene acceptors is mostly unclear. Moreover, the origin of the reduced-Langevin recombination rate in bulk heterojunction solar cells in general is still poorly understood. Here, we investigate the bimolecular recombination rate and charge transport in a series of high-performance organic solar cells based on non-fullerene acceptors. From steady-state dark injection measurements and drift–diffusion simulations of the current–voltage characteristics under illumination, Langevin reduction factors of up to over two orders of magnitude are observed. The reduced recombination is essential for the high fill factors of these solar cells. The Langevin reduction factors are observed to correlate with the quadrupole moment of the acceptors, which is responsible for band bending at the donor–acceptor interface, forming a barrier for charge recombination. Overall these results therefore show that suppressed bimolecular recombination is essential for the performance of organic solar cells and provide design rules for novel materials.

What's Next for Organic Solar Cells? The Frontiers and Challenges

The power conversion efficiency (PCE) of organic solar cells (OSCs) is improved dramatically in recent years and now approaches >19% for single‐junction cells and >20% for tandem cells. Therefore, the practical use of OSCs is becoming a reality. This perspective summarizes the state of the art of OSC characteristics and discusses the challenges that remain in further improving PCE. The short‐circuit current density (J SC) of the state‐of‐the‐art OSCs almost approaches 30 mA cm−2. As the internal quantum efficiencies of these devices exceed 90%, for further improvement in J SC, it is necessary to suppress reflection at interfaces and increase the active layer thickness to absorb as many photons as possible. Further suppression of the nonradiative voltage loss is imperative, as there is still large room for improvement compared to inorganic and perovskite counterparts. Hence, increasing the exciton lifetime and photoluminescence quantum yield of nonfullerene acceptors are pivotal to improving the open‐circuit voltage of OSCs. The fill factors of the latest OSCs approach 80%; however, because the optimized active layer thickness remains ≈100 nm, further suppression of bimolecular charge recombination is needed. Finally, this perspective discusses to what extent PCE can be improved and what can be done to achieve this.

Chain aggregation dictates bimolecular charge recombination and fill factor of all-polymer blend solar cells

Small bimolecular charge recombination coefficients resulted in all-polymer blend solar cells with high fill factors. The preferred blend morphology was characterized by a well-ordered local structure, exhibiting chain aggregation by both the polymer donor and acceptor.

Molecular dispersion enhances photovoltaic efficiency and thermal stability in quasi-bilayer organic solar cells

In comparison to widely adopted bulk heterojunction (BHJ) structures for organic solar cells (OSC), exploiting the sequential deposition to form planar heterojunction (PHJ) structures enables to realize the favorable vertical phase separation to facilitate charge extraction and reduce charge recombination in OSCs. However, effective tunings on the power conversion efficiency (PCE) in PHJ-OSCs are still restrained by the currently available methods. Based on a polymeric donor PBDBT-2F (PBDBT= Poly [[4,8-bis [5-(2-ethylhexyl)-4-fluoro-2-thienyl]benzo [1,2- b :4,5- b ′]dithiophene-2,6-diyl]-2,5-thiophenediyl [5,7-bis (2-ethylhexyl)-4,8-dioxo-4 H ,8 H -benzo [1,2- c :4,5- c ′]dithiophene-1,3-diyl]-2,5-thiophenediyl]) and a non-fullerene (NF) acceptor Y6, we proposed a strategy to improve the properties of photovoltaic performances in PHJ-based OSCs through dilute dispersions of the PBDBT-2F donor into the acceptor-dominant phase with the sequential film deposition. With the control of donor dispersions, the charge transport balance in the PHJ-OSCs is improved, leading to the expedited photocarrier sweep-out with reduced bimolecular charge recombination. As a result, a PCE of 15.4% is achieved in the PHJ-OSCs. Importantly, the PHJ solar cells with donor dispersions exhibit better thermal stability than corresponding BHJ devices, which is related to the better film morphology robustness and less affected charge sweep-out during the thermal aging.

Contrasting Electron and Hole Transfer Dynamics from CH(NH2)2PbI3 Perovskite Quantum Dots to Charge Transport Layers

In this work, the ultrafast transient absorption spectroscopy (TAs) was utilized to first investigate the charge transfer from the emerging FAPbI3 (FA = CH(NH2)2) perovskite quantum dots (PQDs) to charge transport layers. Specifically, we compared the TAs in pure FAPbI3 PQDs, PQDs grown with both electron and hole transfer layers (ETL and HTL), and PQDs with only ETL or HTL. The TA signals induced by photoexcited electrons decay much faster in PQDs samples with the ETL (~20 ps) compared to the pure FAPbI3 PQDs (>1 ns). These results reveal that electrons can effectively transport between coupled PQDs and transfer to the ETL (TiO2) at a time scale of 20 ps, much faster than the bimolecular charge recombination inside the PQDs (>1 ns), and the electron transfer efficiency is estimated to be close to 100%. In contrast, the temporal evolution of the TA signals in the PQDs with and without HTL exhibit negligible change, and no substantive hole transfer to the HTL (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], PTAA) occurs within 1 ns. The much slower hole transfer implies the further potential of increasing the overall photo-carrier conversion efficiency through enhancing the hole diffusion length and fine-tuning the coupling between the HTL and PQDs.

Fast Field-Insensitive Charge Extraction Enables High Fill Factors in Polymer Solar Cells.

Fill factor (FF) is a determining parameter for the power conversion efficiency (PCE) of organic solar cells (OSC). So far, nonfullerene (NF) OSCs with state-of-the-art PCEs exhibit FFs <0.8, lower than the values of Si or perovskite solar cells. The FFs directly display the dependence of photocurrent on bias, meaning that the competition between charge extraction and recombination is modulated by internal electric potential (Vin). Here, we report a study to understand key parameters/properties affecting the device FF based on seven groups of NF-OSCs consisting of widely used PBDBT-2F or PTB7-Th donors and representative NF-acceptors with FFs ranging from 0.60 to 0.78 and PCEs from 10.27 to 16.09%. We used field-dependent transient photocurrent measurements to reveal that fast and field-insensitive charge extraction at low Vin is an essential prerequisite for obtaining high FFs (0.75-0.8), which is enabled by balanced charge transport in steady and reduced bimolecular charge recombination in high purity phases. With bias-dependent quantum efficiency analysis, we further show that the recombination loss at low Vin in the devices with low FFs tends to be more significant involving excitons generated in the donor phase of blends. Our results provide relevance for how to improve the FF toward the boost of photovoltaic performance in NF-OSCs.

Afterglow Effects as a Tool to Screen Emissive Nongeminate Charge Recombination Processes in Organic Photovoltaic Composites.

Disentangling temporally overlapping charge carrier recombination events in organic bulk heterojunctions by optical spectroscopy is challenging. Here, a new methodology for employing delayed luminescence spectroscopy is presented. The proposed method is capable of distinguishing between recombination of spatially separated charge carriers and trap-assisted charge recombination simply by monitoring the delayed luminescence (afterglow) of bulk heterojunctions with a quasi time-integrated detection scheme. Applied on the model composite of the donor poly(6,12-dihydro-6,6,12,12-tetraoctyl-indeno[1,2-b]fluorene-alt-benzothiadiazole) (PIF8BT) polymer and the acceptor ethyl-propyl perylene diimide (PDI) derivative, that is, PIF8BT:PDI, the luminescence of charge-transfer (CT) states created by nongeminate charge recombination on the ns to μs timescale is observed. Fluence-dependent, quasi time-integrated detection of the CT luminescence monitors exclusively emissive charge recombination events, while rejecting the contribution of other early-time emissive processes. Trap-assisted and bimolecular charge recombination channels are identified based on their distinct dependence on fluence. The importance of the two recombination channels is correlated with the layer's order and electrical properties of the corresponding devices. Four different microstructures of the PIF8BT:PDI composite obtained by thermal annealing are investigated. Thermal annealing of PIF8BT:PDI shrinks the PDI domains in parallel with the growth of the PIF8BT domains in the blend. Common to all states studied, the delayed CT luminescence signal is dominated by trap-assisted recombination. Yet, the minor fraction of fully separated charge recombination in the overall CT emission increases as the difference in the size of the donor and acceptor domains in the PIF8BT:PDI blend becomes larger. Electric field-induced quenching measurements on complete PIF8BT:PDI devices confirm quantitatively the dominance of emissive trap-limited charge recombination and demonstrates that only 40% of the PIF8BT/PDI CT luminescence comes from the recombination of fully-separated charges, taking place within 200 ns after photoexcitation. The method is applicable to other nonfullerene acceptor blends beyond the system discussed here, if their CT state luminescence can be monitored.

Long-Lived Free Charge Carriers at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

Semiconducting single-walled carbon nanotubes (s-SWCNTs) have been thoroughly investigated as the components of various photovoltaic cells due to several advantages such as spectral tunability, absence of charge-transfer (CT) states, giant aspect ratio, chemical robustness, and hydrophobicity. In the previous study, it was reported that the heterojunctions between s-SWCNTs and perylene diimide (PDI)-based electron acceptors yield long-lived charge separated states whose lifetimes are more than 1.5 µs. Besides the potential of PDI-based electron acceptors to substitute fullerene-based electron acceptors, this work noted the significance of the molecular geometries of PDI-based electron acceptors which result in molecular aggregation and the associated charge delocalization in the acceptor phase. However, the true characteristics of the long-lived charge carriers for these heterojunctions have not been revealed yet. For instance, the degree to which the charge carriers generated at these heterojunctions are free or trapped was not yet clear. Moreover, it was not determined whether the charge recombination process from these heterojunctions is monomolecular-like or bimolecular-like. In this study, we explored the nature of charge carriers for the heterojunctions between (6,5) s-SWCNTs and two different PDI-based electron acceptors by combining two effective spectroscopic techniques: transient absorption (TA) and time-resolved microwave conductivity (TRMC). Two PDI-based electron acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, were synthesized and coated on (6,5) s-SWCNT films to form donor-acceptor heterojunctions. TA and TRMC studies reveal that the dynamics of the charge-separated states across the (6,5) s-SWCNT/PDI-based acceptor heterojunctions remain similar over three orders of magnitude in absorbed photon flux. This fluence independence of the heterojunctions indicates that the charge carriers recombine ‘pseudo’-monomolecularly. Moreover, the charge recombination kinetics from TA and TRMC studies are well-matched, indicating that most of the generated charge carriers are free, not trapped. The unconventionally strong suppression of bimolecular charge recombination from these heterojunctions, supported by fluence independence of charge recombination dynamics, may be attributed to the high carrier mobility and good charge delocalization in both (6,5) s-SWCNTs and PDI-based acceptors. These factors can also be regarded as the origin of high free charge carrier generation in these heterojunctions. These photophysical studies provide the fundamental understandings of the charge generation process in s-SWCNT-based heterojunctions and how different electron acceptor materials can impact the nature of charge generation with respect to the heterojunction energetics and molecular orientations. The results can inform rational design strategies for s-SWCNT-based optoelectronic applications.

Simple Bithiophene–Rhodanine‐Based Small Molecule Acceptor for Use in Additive‐Free Nonfullerene OPVs with Low Energy Loss of 0.51 eV

AbstractThe introduction of rigid and extended ladder‐type fused‐ring cores, such as indacenodithiophene, has enabled the synthesis of a variety of nonfullerene small molecules for use as electron acceptors in high‐performance organic photovoltaic cells. Contrasting with recent trends, a very simple‐structured nonfullerene acceptor (NFA), T2‐ORH, consisting of a bithiophene core and octyl‐substituted rhodanine ends, is synthesized in two steps from inexpensive commercially available raw materials. Its relatively short π‐conjugation results in a wide bandgap and a blue‐shifted UV–vis absorption profile complementary to those of poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐3‐fluorothieno[3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th). Despite a sufficient offset between T2‐ORH and PTB7‐Th, the lowest unoccupied molecular orbital (LUMO) energy level of T2‐ORH is still higher than the LUMOs of other NFAs (e.g., ITIC). Therefore, the PTB7‐Th:T2‐ORH blend film exhibits an efficiency of 9.33% with a high open‐circuit voltage of 1.07 V and a short‐circuit current of 14.72 mA cm−2 in an additive‐free single‐junction cell. Importantly, the optimized device displays a remarkably low energy loss of 0.51 eV, in which bimolecular and monomolecular charge recombination is effectively suppressed by solvent vapor annealing treatment. The blend film has a very smooth and homogeneous morphology, providing both vertical and parallel charge transport in the devices.

Effect of Post-Thermal Annealing on the Performance and Charge Photogeneration Dynamics of PffBT4T-2OD/PC71BM Solar Cells.

In this work, we studied influence of post thermal annealing on the performance and charge photogeneration processes of PffBT4T-2OD/PC71BM solar cells. As-prepared device exhibits a high-power conversion efficiency of 9.5%, much higher than that after thermal annealing. To understand this phenomenon, we studied charge photogeneration processes in these solar cells by means of time resolved spectroscopy. We associate the degradation of solar cell performance with the reduction of exciton dissociation efficiency and with increased bimolecular recombination of photogenerated charges as a result of annealing. We correlate the generation of localized PffBT4T-2OD polarons observed via spectro-electrochemical measurements with enhancement of the bimolecular charge recombination of annealed solar cells.

Low‐Temperature Processable High‐Performance D–A‐Type Random Copolymers for Nonfullerene Polymer Solar Cells and Application to Flexible Devices

AbstractDonor–acceptor random copolymers incorporating 1,3‐bis(thiophen‐2‐yl)‐5,7‐bis(2‐ethylhexyl)benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione (BDD) and 4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT‐Th) are developed. Nonfullerene solar cells introducing the random copolymer PBDB‐T73 (BDT‐Th:BDD=7:3) 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 are found to exhibit efficiency of 11.14%, which is superior to that of the PBDB‐T alternating copolymer (10.02%). The PBDB‐T73 device exhibits high performance due to low bimolecular charge recombination and good charge transport balance even though none of the treatments that are usually necessary for improving crystalline properties of active layers are performed; in contrast, the PBDB‐T device requires thermal annealing in order to enhance the polymer's crystallinity and obtain improved fill factor and Jsc values. It is demonstrated that efficient charge transport occurs in the PBDB‐T73 blend despite relatively low crystallinity of the polymer. The percolating network structure of the large mixed phase in the PBDB‐T73 blend has an important role in its efficient charge transport. Moreover, due to the low‐temperature processability of PBDB‐T73, flexible PBDB‐T73 solar cell devices prepared on polyethylene terephthalate (PET) substrates exhibit high photovoltaic performance, 10.02%, whereas the efficiency of PBDB‐T‐based flexible devices (7.2%) is significantly lower due to damage to the active layer on indium tin oxide (ITO)/PET that results from thermal annealing.

Multiple Roles of a Non-fullerene Acceptor Contribute Synergistically for High-Efficiency Ternary Organic Photovoltaics

Summary Ternary structure is an important design strategy to obtain high-efficiency non-fullerene organic photovoltaics (OPVs). However, the role of the third component to the standard binary system is still unclear. Here, a wide-bandgap small-molecule acceptor, denoted IDT-T, is synthesized and used together with a wide-bandgap donor polymer, PBDB-T, and a low-bandgap acceptor, ITIC, for fullerene-free ternary solar cells. The ternary cell features an enhanced power conversion efficiency (PCE) up to 12.2%, together with improved photocurrent density, open-circuit voltage (VOC), and fill factor. Studies of the thin films indicate that IDT-T functions as an energy-level mediator, a fluorescence resonance energy-transfer donor, an electron acceptor, and a crystallization modulator in the blend, which contribute synergistically in the ternary blend to deliver a higher VOC, more efficient exciton generation, suppressed bimolecular charge recombination and enhanced charge transport, and an overall high photovoltaic performance.

Transient Photocurrent Elucidating Carrier Dynamics and Potential of Bulk Heterojunction Solar Cells Fabricated by Thermal Precursor Approach

Transient photocurrents are measured to clarify carrier dynamics in a series of bulk heterojunction solar cells that are composed of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) and diketopyrrolopyrrole‐tetrabenzoporphyrin conjugates substituted by straight alkyl groups (Cn‐DPP‐BP), of which the device parameters are largely dependent on the length of the substituted alkyl groups (Cn). The time profile of the observed transients indicates the presence of both unimolecular and bimolecular charge recombination processes in the active layer of the cells. Analysis of the photocurrent decays detected at various bias voltages using a drift model that considers charge extraction by electrodes and charge recombination in the active layer enables elucidation of the charge drift mobility, the initial photocarrier density, and the charge recombination rate constants. The bimolecular recombination rate constant is correlated with Cn and this is the main factor that determines the power conversion efficiency (η) of the Cn‐DPP‐BP:PCBM solar cells. The Cn‐dependent fill factor can be interpreted in terms of the bias voltage dependence of the ratio between the extraction and recombination charges (Qex/Qre). Comparison of η and Qex/Qre at the short‐circuit condition predicts that η for the Cn‐DPP‐BP:PCBM solar cell can be potentially improved up to 6%.