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1.
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.  相似文献   

2.
The best organic solar cells (OSCs) achieve comparable peak external quantum efficiencies and fill factors as conventional photovoltaic devices. However, their voltage losses are much higher, in particular those due to nonradiative recombination. To investigate the possible role of triplet states on the donor or acceptor materials in this process, model systems comprising Zn‐ and Cu‐phthalocyanine (Pc), as well as fluorinated versions of these donors, combined with C60 as acceptor are studied. Fluorination allows tuning the energy level alignment between the lowest energy triplet state (T1) and the charge‐transfer (CT) state, while the replacement of Zn by Cu as the central metal in the Pcs leads to a largely enhanced spin–orbit coupling. Only in the latter case, a substantial influence of the triplet state on the nonradiative voltage losses is observed. In contrast, it is found that for a large series of typical OSC materials, the relative energy level alignment between T1 and the CT state does not substantially affect nonradiative voltage losses.  相似文献   

3.
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.  相似文献   

4.
The electron–hole recombination kinetics of organic photovoltaics (OPVs) are known to be sensitive to the relative energies of triplet and charge‐transfer (CT) states. Yet, the role of exciton spin in systems having CT states above 1.7 eV—like those in near‐ultraviolet‐harvesting OPVs—has largely not been investigated. Here, aggregation‐induced room‐temperature intersystem crossing (ISC) to facilitate exciton harvesting in OPVs having CT states as high as 2.3 eV and open‐circuit voltages exceeding 1.6 V is reported. Triplet excimers from energy‐band splitting result in ultrafast CT and charge separation with nonradiative energy losses of <250 meV, suggesting that a 0.1 eV driving force is sufficient for charge separation, with entropic gain via CT state delocalization being the main driver for exciton dissociation and generation of free charges. This finding can inform engineering of next‐generation active materials and films for near‐ultraviolet OPVs with open‐circuit voltages exceeding 2 V. Contrary to general belief, this work reveals that exclusive and efficient ISC need not require heavy‐atom‐containing active materials. Molecular aggregation through thin‐film processing provides an alternative route to accessing 100% triplet states on photoexcitation.  相似文献   

5.
Charge‐transfer (CT) state electroluminescence is investigated in several polymer:fullerene bulk heterojunction solar cells. The ideality factor of the electroluminescence reveals that the CT emission in polymer:fullerene solar cells originates from free‐carrier bimolecular recombination at the donor‐acceptor interface, rather than a charge‐trap‐mediated process. The fingerprint of the presence of nonradiative trap‐assisted recombination, a voltage‐dependent CT electroluminescence quantum efficiency, is only observed for the P3HT:PCBM system, which is explained by a reduction of the competing bimolecular recombination rate. These results are in agreement with measurements of the illumination‐intensity dependence of the open‐circuit voltage.  相似文献   

6.
Achieving the highest power conversion efficiencies in bulk heterojunction organic solar cells requires a morphology that delivers electron and hole percolation pathways for optimized transport, plus sufficient donor:acceptor contact area for near unity charge transfer state formation. This is a significant structural challenge, particularly in semiconducting polymer:fullerene systems. This balancing act in the model high efficiency PTB7:PC70BM blend is studied by tuning the donor:acceptor ratio, with a view to understanding the recombination loss mechanisms above and below the fullerene transport percolation threshold. The internal quantum efficiency is found to be strongly correlated to the slower carrier mobility in agreement with other recent studies. Furthermore, second‐order recombination losses dominate the shape of the current density–voltage curve in efficient blend combinations, where the fullerene phase is percolated. However, below the charge transport percolation threshold, there is an electric‐field dependence of first‐order losses, which includes electric‐field‐dependent photogeneration. In the intermediate regime, the fill factor appears to be limited by both first‐ and second‐order losses. These findings provide additional basic understanding of the interplay between the bulk heterojunction morphology and the order of recombination in organic solar cells. They also shed light on the limitations of widely used transport models below the percolation threshold.  相似文献   

7.
Even though significant breakthroughs with over 18% power conversion efficiencies (PCEs) in polymer:non‐fullerene acceptor (NFA) bulk heterojunction organic solar cells (OSCs) have been achieved, not many studies have focused on acquiring a comprehensive understanding of the underlying mechanisms governing these systems. This is because it can be challenging to delineate device photophysics in polymer:NFA blends comprehensively, and even more complicated to trace the origins of the differences in device photophysics to the subtle differences in energetics and morphology. Here, a systematic study of a series of polymer:NFA blends is conducted to unify and correlate the cumulative effects of i) voltage losses, ii) charge generation efficiencies, iii) non‐geminate recombination and extraction dynamics, and iv) nuanced morphological differences with device performances. Most importantly, a deconvolution of the major loss processes in polymer:NFA blends and their connections to the complex BHJ morphology and energetics are established. An extension to advanced morphological techniques, such as solid‐state NMR (for atomic level insights on the local ordering and donor:acceptor π? π interactions) and resonant soft X‐ray scattering (for donor and acceptor interfacial area and domain spacings), provide detailed insights on how efficient charge generation, transport, and extraction processes can outweigh increased voltage losses to yield high PCEs.  相似文献   

8.
Molecular dynamics simulations are combined with density functional theory calculations to evaluate the impact of static and dynamic disorders on the energy distribution of charge‐transfer (CT) states at donor–acceptor heterojunctions, such as those found in the active layers of organic solar cells. It is shown that each of these two disorder components can be partitioned into contributions related to the energetic disorder of the transport states and to the disorder associated with the hole–electron electrostatic interaction energies. The methodology is applied to evaluate the energy distributions of the CT states in representative bulk heterojunctions based on poly‐3‐hexyl‐thiophene and phenyl‐C61‐butyric‐acid methyl ester. The results indicate that the torsional fluctuations of the polymer backbones are the main source of both static and dynamic disorders for the CT states as well as for the transport levels. The impact of static and dynamic disorders on radiative and nonradiative geminate recombination processes is also discussed.  相似文献   

9.
In organic photovoltaic (PV) cells, the well‐established donor‐acceptor (D/A) concept enabling photo‐induced charge transfer between two partners with suitable energy level alignment has proven extremely successful. Nevertheless, the introduction of such a heterojunction is accompanied with additional energy losses as compared to an inorganic homojunction cell, owing to the presence of a charge‐transfer (CT) state at the D/A interface. Based on the principle of detailed balance, a modified Shockley‐Queisser theory is developed including the essential effects of interfacial CT states, that allows for a quantitative assessment of the thermodynamic efficiency limits of molecular D/A solar cells. Key parameters, apart from the optical gap of the absorber material, entering the model are the energy (ECT) and relative absorption strength (αCT) of the CT state. It is demonstrated how the open‐circuit voltage (VOC) and thus the power conversion efficiency are affected by different parameter values. Furthermore, it is shown that temperature dependent device characteristics can serve to determine the CT energy, and thus the upper limit of VOC for a given D/A combination, as well as to quantify non‐radiative recombination losses. The model is applied to diindenoperylene (DIP)‐based photovoltaic devices, with open‐circuit voltages between 0.9 and 1.4 V, depending on the partner, that have recently been reported.  相似文献   

10.
How free charge is generated at organic donor–acceptor interfaces is an important question, as the binding energy of the lowest energy (localized) charge transfer states should be too high for the electron and hole to escape each other. Recently, it has been proposed that delocalization of the electronic states participating in charge transfer is crucial, and aggregated or otherwise locally ordered structures of the donor or the acceptor are the precondition for this electronic characteristic. The effect of intermolecular aggregation of both the polymer donor and fullerene acceptor on charge separation is studied. In the first case, the dilute electron acceptor triethylsilylhydroxy‐1,4,8,11,15,18,22,25‐octabutoxyphthalocyaninatosilicon(IV) (SiPc) is used to eliminate the influence of acceptor aggregation, and control polymer order through side‐chain regioregularity, comparing charge generation in 96% regioregular (RR‐) poly(3‐hexylthiophene) (P3HT) with its regiorandom (RRa‐) counterpart. In the second case, ordered phases in the polymer are eliminated by using RRa‐P3HT, and phenyl‐C61‐butyric acid methyl ester (PC61BM) is used as the acceptor, varying its concentration to control aggregation. Time‐resolved microwave conductivity, time‐resolved photoluminescence, and transient absorption spectroscopy measurements show that while ultrafast charge transfer occurs in all samples, long‐lived charge carriers are only produced in films with intermolecular aggregates of either RR‐P3HT or PC61BM, and that polymer aggregates are just as effective in this regard as those of fullerenes.  相似文献   

11.
A new strategy for designing ternary solar cells is reported in this paper. A low‐bandgap polymer named PTB7‐Th and a high‐bandgap polymer named PBDTTS‐FTAZ sharing the same bulk ionization potential and interface positive integer charge transfer energy while featuring complementary absorption spectra are selected. They are used to fabricate efficient ternary solar cells, where the hole can be transported freely between the two donor polymers and collected by the electrode as in one broadband low bandgap polymer. Furthermore, the fullerene acceptor is chosen so that the energy of the positive integer charge transfer state of the two donor polymers is equal to the energy of negative integer charge transfer state of the fullerene, enabling enhanced dissociation of all polymer donor and fullerene acceptor excitons and suppressed bimolecular and trap assistant recombination. The two donor polymers feature good miscibility and energy transfer from high‐bandgap polymer of PBDTTS‐FTAZ to low‐bandgap polymer of PTB7‐Th, which contribute to enhanced performance of the ternary solar cell.  相似文献   

12.
The origin of photocurrent losses in the power‐generating regime of organic solar cells (OSCs) remains a controversial topic, although recent literature suggests that the competition between bimolecular recombination and charge extraction determines the bias dependence of the photocurrent. Here the steady‐state recombination dynamics is studied in bulk‐heterojunction OSCs with different hole mobilities from short‐circuit to maximum power point. It is shown that in this regime, in contrast to previous transient extracted charge and absorption spectroscopy studies, first‐order recombination outweighs bimolecular recombination of photogenerated charge carriers. This study demonstrates that the first‐order losses increase with decreasing slower carrier mobility, and attributes them to either mobilization of charges trapped at the donor:acceptor interface through the Poole–Frenkel effect, and/or recombination of photogenerated and injected charges. The dependence of both first‐order and higher‐order losses on the slower carrier mobility explains why the field dependence of OSC efficiencies has historically been attributed to charge‐extraction losses.  相似文献   

13.
Bimolecular recombination in bulk heterojunction organic solar cells is the process by which nongeminate photogenerated free carriers encounter each other, and combine to form a charge transfer (CT) state which subsequently relaxes to the ground state. It is governed by the diffusion of the slower and faster carriers toward the electron donor–acceptor interface. In an increasing number of systems, the recombination rate constant is measured to be lower than that predicted by Langevin's model for relative Brownian motion and the capture of opposite charges. This study investigates the dynamics of charge generation, transport, and recombination in a nematic liquid crystalline donor:fullerene acceptor system that gives solar cells with initial power conversion efficiencies of >9.5%. Unusually, and advantageously from a manufacturing perspective, these efficiencies are maintained in junctions thicker than 300 nm. Despite finding imbalanced and moderate carrier mobilities in this blend, strongly suppressed bimolecular recombination is observed, which is ≈150 times less than predicted by Langevin theory, or indeed, more recent and advanced models that take into account the domain size and the spatial separation of electrons and holes. The suppressed bimolecular recombination arises from the fact that ground‐state decay of the CT state is significantly slower than dissociation.  相似文献   

14.
The incorporation of multiple donors into the bulk‐heterojunction layer of organic polymer solar cells (PSCs) has been demonstrated as a practical and elegant strategy to improve photovoltaics performance. However, it is challenging to successfully design and blend multiple donors, while minimizing unfavorable interactions (e.g., morphological traps, recombination centers, etc.). Here, a new Förster resonance energy transfer‐based design is shown utilizing the synergistic nature of three light active donors (two small molecules and a high‐performance donor–acceptor polymer) with a fullerene acceptor to create highly efficient quaternary PSCs with power conversion efficiencies (PCEs) of up to 10.7%. Within this quaternary architecture, it is revealed that the addition of small molecules in low concentrations broadens the absorption bandwidth, induces cocrystalline molecular conformations, and promotes rapid (picosecond) energy transfer processes. These results provide guidance for the design of multiple‐donor systems using simple processing techniques to realize single‐junction PSC designs with unprecedented PCEs.  相似文献   

15.
Triplet exciton (TE) formation pathways are systematically investigated in prototype bulk heterojunction (BHJ) “super yellow” poly(p‐phenylene vinylene) (SY‐PPV) solar cell devices with varying fullerene compositions using complementary optoelectrical and electrically detected magnetic resonance (EDMR) spectroscopies. It is shown that EDMR spectroscopy allows the unambiguous demonstration of fullerene triplet production in BHJ polymer:fullerene solar cells. EDMR triplet detection under selective photoexcitation of each blend component and of the interfacial charge transfer (CT) state reveals that low lying fullerene TEs are produced by direct intersystem crossing from singlet excitons (SEs). The direct CT‐TE recombination pathway, although energetically feasible, is kinetically suppressed in these devices. However, high energy CT states in the CT manifold can contribute to the population of the fullerene triplet state via a direct CT‐SE conversion. This undesirable energetic alignment could be one of the causes for the severe reduction in photocurrent observed when the open‐circuit voltage of polymer:fullerene solar cells is pushed to 1.0 V or beyond.  相似文献   

16.
Three different theoretical approaches are presented to identify pathways to organic solar cells with power conversion efficiencies in excess of 20%. A radiation limit for organic solar cells is introduced that elucidates the role of charge‐transfer (CT) state absorption. Provided this CT action is sufficiently weak, organic solar cells can be as efficient as their inorganic counterparts. Next, a model based on Marcus theory of electronic transfer that also considers exciton generation in both the electron donor and electron acceptor is used to show how reduction of the reorganization energies can lead to substantial efficiency gains. Finally, the dielectric constant is introduced as a central parameter for efficient solar cells. By using a drift–diffusion model, it is found that efficiencies of more than 20% are within reach.  相似文献   

17.
Organic solar cells lag behind their inorganic counterparts in efficiency due largely to low open‐circuit voltages (Voc). In this work, a comprehensive framework for understanding and improving the open‐circuit voltage of organic solar cells is developed based on equilibrium between charge transfer (CT) states and free carriers. It is first shown that the ubiquitous reduced Langevin recombination observed in organic solar cells implies equilibrium and then statistical mechanics is used to calculate the CT state population density at each voltage. This general result permits the quantitative assignment of Voc losses to a combination of interfacial energetic disorder, non‐negligible CT state binding energies, large degrees of mixing, and sub‐ns recombination at the donor/acceptor interface. To quantify the impact of energetic disorder, a new temperature‐dependent CT state absorption measurement is developed. By analyzing how the apparent CT energy varies with temperature, the interfacial disorder can be directly extracted. 63–104 meV of disorder is found in five systems, contributing 75–210 mV of Voc loss. This work provides an intuitive explanation for why qVoc is almost always 500–700 meV below the energy of the CT state and shows how the voltage can be improved.  相似文献   

18.
All‐polymer solar cells (all‐PSCs) utilizing p‐type polymers as electron‐donors and n ‐typepolymers as electron‐acceptors have attracted a great deal of attention, and their efficiencies have been improved considerably. Here, five polymer donors with different molecular orientations are synthesized by random copolymerization of 5‐fluoro‐2,1,3‐benzothiadiazole with different relative amounts of 2,2′‐bithiophene (2T) and dithieno[3,2‐b;2′,3′‐d]thiophene (DTT). Solar cells are prepared by blending the polymer donors with a naphthalene diimide‐based polymer acceptor (PNDI) or a [6,6]‐phenyl C71‐butyric acid methyl ester (PC71BM) acceptor and their morphologies and crystallinity as well as optoelectronic, charge‐transport and photovoltaic properties are studied. Interestingly, charge generation in the solar cells is found to show higher dependence on the crystal orientation of the donor polymer for the PNDI‐based all‐PSCs than for the conventional PC71BM‐based PSCs. As the population of face‐on‐oriented crystallites of the donor increased in PNDI‐based PSC, the short‐circuit current density (JSC) and external quantum efficiency of the devices are found to significantly improve. Consequently, device efficiency was enhanced of all‐PSC from 3.11% to 6.01%. The study reveals that producing the same crystal orientation between the polymer donor and acceptor (face‐on/face‐on) is important in all‐PSCs because they provide efficient charge transfer at the donor/acceptor interface.  相似文献   

19.
A series of narrow bandgap electron acceptors is designed and synthesized for efficient near‐infrared (NIR) organic solar cells. Extending π‐conjugation of donor frameworks leads to an intense intramolecular charge transfer, resulting in broad absorption profiles with band edge reaching 950 nm. When blended with an electron donor polymer PTB7‐Th, IOTIC‐2F exhibits efficient charge transfer even with a small energetic offset, so as to achieve a large photogenerated current over 22 mA cm?2 with small energy losses (≈0.49 eV) in solar cell devices. With an intense NIR absorbance, PTB7‐Th:IOTIC‐2F‐based cells achieve a power conversion efficiency of 12.1% with good visible transparency (52% transmittance from 370 to 740 nm). Analysis of film morphology reveals that processing with solvent additives enhances crystalline features of acceptor components, while keeping an appropriate level of donor:acceptor intermixing in the binary blends. The incorporation of the third component, ITIC‐2F, into the PTB7‐Th:IOTIC‐2F blends increases the device efficiency up to 12.9%. The improvement is assigned to the cascaded energy‐level structure and desirable nanoscale phase separation of the ternary blends, which is beneficial to the photocurrent generation. This work provides an efficient molecular design strategy to optimize nonfullerene acceptor properties for efficient NIR organic photovoltaics.  相似文献   

20.
Polymer:fullerene solar cells are demonstrated with power conversion efficiencies over 7% with blends of PBDTTPD and PC61BM. These devices achieve open‐circuit voltages (Voc) of 0.945 V and internal quantum efficiencies of 88%, making them an ideal candidate for the large bandgap junction in tandem solar cells. Voc’s above 1.0 V are obtained when the polymer is blended with multiadduct fullerenes; however, the photocurrent and fill factor are greatly reduced. In PBDTTPD blends with multiadduct fullerene ICBA, fullerene emission is observed in the photoluminescence and electroluminescence spectra, indicating that excitons are recombining on ICBA. Voltage‐dependent, steady state and time‐resolved photoluminescence measurements indicate that energy transfer occurs from PBDTTPD to ICBA and that back hole transfer from ICBA to PBDTTPD is inefficient. By analyzing the absorption and emission spectra from fullerene and charge transfer excitons, we estimate a driving free energy of –0.14 ± 0.06 eV is required for efficient hole transfer. These results suggest that the driving force for hole transfer may be too small for efficient current generation in polymer:fullerene solar cells with Voc values above 1.0 V and that non‐fullerene acceptor materials with large optical gaps (>1.7 eV) may be required to achieve both near unity internal quantum efficiencies and values of Voc exceeding 1.0 V.  相似文献   

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