The Effect of Ageing on Exciton Dynamics,Charge Separation,and Recombination in P3HT/PCBM Photovoltaic Blends

A study of how light‐induced degradation influences the fundamental photophysical processes in the active layer of poly(3‐hexylthiophene)/[6,6]‐phenyl C₆₁‐butyric acid methyl ester (P3HT/PCBM) solar cells is presented. Non‐encapsulated samples are systematically aged by exposure to AM 1.5 illumination in the presence of dry air for different periods of time. The extent of degradation is quantified by the relative loss in the absorption maximum of the P3HT, which is varied in the range 0% to 20%. For degraded samples an increasing loss in the number of excitons within the P3HT domains is observed with longer ageing periods. This loss occurs rapidly, within the first 15 ps after photoexcitation. A more pronounced decrease in the population of polarons than excitons is observed, which also occurs on a timescale of a few picoseconds. These observations, complemented by a quantitative analysis of the polaron and exciton population dynamics, unravel two primary loss mechanisms for the performances of aged P3HT/PCBM solar cells. One is an initial ultrafast decrease in the polaron generation, apparently not related to the exciton diffusion to the polymer/fullerene interface; the second, less significant, is a loss in the exciton population within the photoexcited P3HT domains. The steady‐state photoinduced absorption spectra of degraded samples exhibits the appearance of a signal ascribed to triplet excitons, which is absent for non‐degraded samples. This latter observation is interpreted considering the formation of degraded sites where intersystem crossing and triplet exciton formation is more effective. The photovoltaic characteristics of same blends are also studied and discussed by comparing the decrease in the overall power conversion efficiency of solar cells.     

Charge Transfer Excitons in Polymer/Fullerene Blends: The Role of Morphology and Polymer Chain Conformation

Here, it is shown how carrier recombination through charge transfer excitons between conjugated polymers and fullerene molecules is mainly controlled by the intrachain conformation of the polymer, and to a limited extent by the mesoscopic morphology of the blend. This experimental result is obtained by combining near‐infrared photoluminescence spectroscopy and transmission electron microscopy, which are sensitive to charge transfer exciton emission and morphology, respectively. The photoluminescence intensity of the charge transfer exciton is correlated to the degree of intrachain order of the polymer, highlighting an important aspect for understanding and limiting carrier recombination in organic photovoltaics.     

Highly Efficient Microscopic Charge Transport within Crystalline Domains in a Furan‐Flanked Diketopyrrolopyrrole‐Based Conjugated Copolymer

Elucidating the interrelation between the molecular structure and charge transport properties in conjugated polymer thin films is an essential issue in developing the design principle of high‐performance polymer materials for application in organic electronics. In particular, the backbone planarity is suggested to be a key element that governs the transport performance, especially in recently developed donor–acceptor (D–A)‐type copolymers exhibiting high mobility, whereas the direct evaluation of the intrinsic transport performance, usually realized only within the small crystalline domains, is difficult by using conventional macroscopic measurements. Here, it is demonstrated that a D–A type copolymer, PDPPF‐DTT, which consists of furan‐flanked diketopyrrolopyrrole (DPP) and dithienothiophene (DTT) units in the conjugated backbone, exhibits a highly efficient charge transport performance within the crystalline domains with a remarkably low activation energy of less than 8 meV, based on microscopic measurements using field‐induced electron spin resonance spectroscopy. This high transport performance is primarily caused by the high backbone planarity realized by introducing furan‐flanked DPP and fused dithienothiophene units, which is demonstrated from the density functional theory calculations. This result provides a microscopic indication of the effectiveness of the present molecular design to produce a planar backbone and realize highly efficient charge transport performance.     

Carrier Tunneling from Charge Transfer States in Organic Photovoltaic Cells

Charge transfer (CT) states play a key role in the functioning of organic solar cells; however, understanding the mechanism by which CT states dissociate efficiently into free charges remain a conceptual challenge. Here, the electric field dependent dynamics of charge generation in planar cyanine/fullerene photovoltaic cells is probed over a wide temperature range using time-resolved Stark effect experiments, transient absorption, and photocurrent measurements. Results indicate that dissociation of thermalized CT states is the rate-limiting step for all temperatures. The dissociation rate strongly depends on the field, but is temperature independent. The results also suggest that the yield of generated charges is temperature independent. Model electrostatic calculations illustrate that specific orientations of the cyanine crystal relative to C₆₀ create a repulsive potential for an electron near the interface that is largely due to the quadrupole moment of the unit cell. In combination with the electron-hole coulomb attraction and the electric field-induced barrier lowering, a high-energy potential barrier forms with a narrow width of a few nanometers. It is proposed that charge separation occurs via a field-dependent electron tunneling mechanism through that barrier, which is temperature independent. The results support a thus far overlooked pathway for CT state dissociation via carrier tunneling.     

Linking Group Influences Charge Separation and Recombination in All‐Conjugated Block Copolymer Photovoltaics

All‐conjugated block copolymers bring together hole‐ and electron‐conductive polymers and can be used as the active layer of solution‐processed photovoltaic devices, but it remains unclear how molecular structure, morphology, and electronic properties influence performance. Here, the role of the chemical linker is investigated through analysis of two donor–linker–acceptor block copolymers that differ in the chemistry of the linking group. Device studies show that power conversion efficiencies differ by a factor of 40 between the two polymers, and ultrafast transient absorption measurements reveal charge separation only in block copolymers that contain a wide bandgap monomer at the donor–acceptor interface. Optical measurements reveal the formation of a low‐energy excited state when donor and acceptor blocks are directly linked without this wide bandgap monomer. For both samples studied, it is found that the rate of charge recombination in these systems is faster than in poly­mer–polymer and polymer–fullerene blends. This work demonstrates that the linking group chemistry influences charge separation in all‐conjugated block copolymer systems, and further improvement of photovoltaic performance may be possible through optimization of the linking group. These results also suggest that all‐conjugated block copolymers can be used as model systems for the donor–acceptor interface in bulk heterojunction blends.     

聚合物光诱导电荷转移光电池的研究进展

综述了以共轭聚合物作为电子施主和 C6 0 及其衍生物作为电子受主的共混与多层器件结构的聚合物光诱导电荷转移光电池的研究进展。对这类新型结构的光电池的基本性能及机制作了介绍。低生产成本、能通过简单甩膜或印刷方式就能制备大面积器件的优势使聚合物光电池在许多实际应用领域具有广阔的前景。对今后进一步提高这类光电池的能量转换效率的研究方向进行了探讨     

Nature of Charge Carriers in a High Electron Mobility Naphthalenediimide Based Semiconducting Copolymer

The nature of charge carriers in recently developed high mobility semiconducting donor‐acceptor polymers is debated. Here, localization due to charge relaxation is investigated in a prototypal system, a good electron transporting naphthalenediimide based copolymer, by means of current‐voltage I‐V electrical characteristics and charge modulation spectroscopy (CMS) in top‐gate field‐effect transistors (FETs), combined with density functional theory (DFT) and time dependent DFT (TDDFT) calculations. In particular, pristine copolymer films are compared with films that underwent a melt‐annealing process, the latter leading to a drastic change of the microstructure. Despite the packing modification, which involves also the channel region, both the electron mobility and the energy of polaronic transitions are substantially unchanged upon melt‐annealing. The polaron absorption features can be rationalized and reproduced by TDDFT calculations for isolated charged oligomers. Therefore, it is concluded that in such a high electron mobility copolymer the charge transport process involves polaronic species which are intramolecular in nature and, from a more general point of view, that interchain delocalization of the polaron is not necessary to sustain charge mobilities in the 0.1 to 1 cm² V^{– 1} s^–1 range. These findings contribute to the rationalization of the charge transport process in the recently developed class of donor‐acceptor π‐conjugated copolymers featuring high charge mobilities and complex morphologies.     

Effect of Charge Density on Energy‐Transfer Properties of Cationic Conjugated Polymers

Cationic conjugated polymers (CCPs) with different charge densities are synthesized via Suzuki polymerization. The CCPs show similar optical properties in aqueous solutions but obvious difference in fluorescence resonance energy transfer (FRET) to Texas Red‐labeled single‐stranded DNA (ssDNA‐TR). Both CCP and TR fluorescence quenching are revealed to influence the energy‐transfer process. The difference in quantum yields of CCP/ssDNA complexes highlights the importance of polymer side‐chain structures and charge density. A CCP with a high charge density and ethylene oxide as the side chain provides the highest quantum yield for CCP/ssDNA complexes, which favors FRET. TR quenching within the CCP/ssDNA complexes is predominantly determined by the CCP charge density. In contrast to the other two polymers, the CCP with low charge density provides the most‐intense polymer‐sensitized TR emission, which is due to the collective response of more optically active polymer units around TR and the minimized TR self‐quenching within the CCP/ssDNA‐TR complexes. These studies provide a new guideline for improving the signal amplification of conjugated‐polymer‐based optical sensors.     

Eleven‐Membered Fused‐Ring Low Band‐Gap Polymer with Enhanced Charge Carrier Mobility and Photovoltaic Performance

A multi‐ring, ladder‐type low band‐gap polymer (PIDTCPDT‐DFBT) is developed to show enhanced light harvesting, charge transport, and photovoltaic performance. It possesses excellent planarity and enhanced effective conjugation length compared to the previously reported fused‐ring polymers. In order to understand the effect of extended fused‐ring on the electronic and optical properties of this polymer, a partially fused polymer PIDTT‐T‐DFBT is also synthesized for comparison. The fully rigidified polymer provides lower reorganizational energy, resulting in one order higher hole mobility than the reference polymer. The device made from PIDTCPDT‐DFBT also shows a quite promising power conversion efficiency of 6.46%. Its short‐circuit current (14.59 mA cm^?2) is also among the highest reported for ladder‐type polymers. These results show that extending conjugation length in fused‐ring ladder polymers is an effective way to reduce band‐gap and improve charge transport for efficient photovoltaic devices.     

Quantification of Temperature-Dependent Charge Separation and Recombination Dynamics in Non-Fullerene Organic Photovoltaics

Transient optical spectroscopy is used to quantify the temperature-dependence of charge separation and recombination dynamics in P3TEA:SF-PDI₂ and PM6:Y6, two non-fullerene organic photovoltaic (OPV) systems with a negligible driving force and high photocurrent quantum yields. By tracking the intensity of the transient electroabsorption response that arises upon interfacial charge separation in P3TEA:SF-PDI₂, a free charge generation rate constant of ≈2.4 × 10¹⁰ s⁻¹ is observed at room temperature, with an average energy of ≈230 meV stored between the interfacial charge pairs. Thermally activated charge separation is also observed in PM6:Y6, and a faster charge separation rate of ≈5.5 × 10¹⁰ s⁻¹ is estimated at room temperature, which is consistent with the higher device efficiency. When both blends are cooled down to cryogenic temperature, the reduced charge separation rate leads to increasing charge recombination either directly at the donor-acceptor interface or via the emissive singlet exciton state. A kinetic model is used to rationalize the results, showing that although photogenerated charges have to overcome a significant Coulomb potential to generate free carriers, OPV blends can achieve high photocurrent generation yields given that the thermal dissociation rate of charges outcompetes the recombination rate.     

Charge Generation at Polymer/Metal Oxide Interface: from Molecular Scale Dynamics to Mesoscopic Effects

The correlation between molecular scale morphology and charge generation across hybrid photovoltaic interfaces made of metal oxides (ZnO and TiO₂) and a prototypical electron donor polymer, P3HT, is investigated. Device characterization and UV‐NIR transient absorption spectroscopy are used to demonstrate that the local disorder of the polymer chains on the surface of the metal–oxide film provides better electron injection efficiencies than the crystalline phases, though the latter are essential for energy and charge transport. An unambiguous spectroscopic tool is also demonstrated to probe the occupation of the conduction band of ZnO following the electron injection from the polymer through the ultrafast tracking of the Burstein‐Moss effect.     

Charge Recombination Dynamics in Organic Photovoltaic Systems with Enhanced Dielectric Constant

Increasing the dielectric constant of organic photovoltaic materials to reduce recombination rates has long been pursued, however, material modification often results in the modification of multiple device characteristics, making system comparison difficult. In this study, a fullerene derivative with an increased blend dielectric constant is examined by the addition of a triethylene glycol appendage to the fullerene (TEG‐PCBM). Density functional theory calculations show a small change to the permanent dipole moment between TEG‐PCBM and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₀BM) resulting in similar solubility, morphology, and device performance. TEG‐PCBM is blended with donors P3HT and PTB7‐Th and a comparable performance to PC₆₀BM is found. This model system shows the rarely reported characteristic of an increase in the dielectric constant while leaving its other properties unaltered. Looking at light intensity effects on open‐circuit voltage (V_oc), short‐circuit current (J_sc), and fill factor (FF) along with exciton dissociation efficiency, it is observed that when switching to the TEG‐ modified fullerene derivative, geminate recombination is not reduced, and Shockley–Read–Hall recombination is increased. While triethlyene glycol appendages may prove to be ineffective in improving recombination through increased dielectric constant, an approach for studying recombination in future high dielectric systems is provided.     

Temperature‐Dependent Aggregation Donor Polymers Enable Highly Efficient Sequentially Processed Organic Photovoltaics Without the Need of Orthogonal Solvents

The conventional method to prepare bulk‐heterojunction organic photovoltaics (OPVs) is a one‐step method from the blend solution of donor and acceptor materials, known as blend‐casting (BC). Recently, an alternative method was demonstrated to achieve high efficiencies (13%) comparable to state‐of‐the‐art BC devices. This two‐step‐coating method, known as “sequential processing,” (SqP) involves sequential deposition of the donor and then the acceptor from two orthogonal solvents. However, the requirement of orthogonal solvents to process the donor and acceptor constrains the choice of materials and processing solvents. In this paper, an improved version of SqP method without the need for using orthogonal solvents is reported. The success is based on donor polymers with strong temperature‐dependent aggregation properties whose solution can be processed at a high temperature, but the resulting film becomes completely insoluble at room temperature, which allows for the processing of overlying acceptors from a wide range of nonorthogonal solvents. With this approach, efficient SqP OPVs is demonstrated based on a range of donor/acceptor materials and processing solvents, and, in every single case, SqP OPVs can outperform their BC counterparts. The results broaden the solvent choices and open a much larger window to optimize the processing parameters of SqP method.     

Material Crystallinity as a Determinant of Triplet Dynamics and Oxygen Quenching in Donor Polymers for Organic Photovoltaic Devices

This paper is concerned with the photophysics of triplet excitons in conjugated donor polymers, and their quenching by molecular oxygen. These photophysics are assayed by transient absorption spectroscopy, and correlated with X‐ray diffraction measurements of relative material crystallinity. Eleven different donor polymers are considered, including representatives from several classes of donor polymers recently developed for organic solar cell applications. Triplet lifetimes in an inert (nitrogen) environment range from <100 ns to 5 μs. A remarkably quantitative correlation is observed between these triplet lifetimes and polymer XRD strength, with more crystalline polymers exhibiting shorter triplet lifetimes. Given the broad range of polymers considered, this correlation indicates that material crystallinity is the dominant factor determining triplet lifetime for the polymers studied herein. The rate constant for oxygen quenching of these triplet states, determined from a comparison of transient absorption data under inert and oxygen environments, also show a correlation with material crystallinity. Overall these dependencies result in the yield of oxygen quenching of polymer triplet states increasing strongly as the crystallinity of the polymer is reduced. These photophysical data are compared with photochemical stability of these donor polymers, assayed by photobleaching studies of polymer films under continuous light exposure in an oxygen environment. A partial correlation is observed, with the most stable polymers being the most crystalline, exhibiting negligible oxygen quenching yields. These results are discussed in terms of the likely origins of the correlations between material crystallinity and photophysics, and in terms of their implications for the environmental stability of such donor polymers in optoelectronic devices.     

Impedance Measurements as a Simple Tool to Control the Quality of Conjugated Polymers Designed for Photovoltaic Applications

The problem of batch‐to‐batch variation of electronic properties and purity of conjugated polymers used as electron donor and photon harvesting materials in organic solar cells is addressed. A simple method is developed for rapid analysis of electronic quality of polymer‐based materials. It is shown that appearance of impurities capable of charge trapping changes electrophysical properties of conjugated polymers. In particular, a clear correlation between the effective relaxation time τeff and relative photovoltaic performance (η/η_max) is revealed for samples of poly(3‐hexylthiophene) intentionally polluted with a palladium catalyst. This dependence is also valid for all other investigated samples of conjugated polymers. Therefore, fast impedance measurements at three different frequencies allow one to draw conclusions about the purity of the analyzed polymer sample and even estimate its photovoltaic performance. The developed method might find extensive applications as a simple tool for product quality control in the laboratory and industrial‐scale production of conjugated polymers for electronic applications.     

Charge Transport and Recombination in Polyspirobifluorene Blue Light‐Emitting Diodes

The charge transport in blue light‐emitting polyspirobifluorene is investigated by both steady‐state current‐voltage measurements and transient electroluminescence. Both measurement techniques yield consistent results and show that the hole transport is space‐charge limited. The electron current is found to be governed by a high intrinsic mobility in combination with electron traps. Numerical simulations on light‐emitting diodes reveal a shift in the recombination zone from the cathode to the anode with increasing bias.     

Controllable Molecular Doping and Charge Transport in Solution‐Processed Polymer Semiconducting Layers

Here, controlled p‐type doping of poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylene vinylene) (MEH‐PPV) deposited from solution using tetrafluoro‐tetracyanoquinodimethane (F4‐TCNQ) as a dopant is presented. By using a co‐solvent, aggregation in solution can be prevented and doped films can be deposited. Upon doping the current–voltage characteristics of MEH‐PPV‐based hole‐only devices are increased by several orders of magnitude and a clear Ohmic behavior is observed at low bias. Taking the density dependence of the hole mobility into account the free hole concentration due to doping can be derived. It is found that a molar doping ratio of 1 F4‐TCNQ dopant per 600 repeat units of MEH‐PPV leads to a free carrier density of 4 × 10²² m^?3. Neglecting the density‐dependent mobility would lead to an overestimation of the free hole density by an order of magnitude. The free hole densities are further confirmed by impedance measurements on Schottky diodes based on F4‐TCNQ doped MEH‐PPV and a silver electrode.     

Ultrafast Hole‐Transfer Dynamics in Polymer/PCBM Bulk Heterojunctions

Ultrafast dynamics of the hole‐transfer process from methanofullerene to a polymer in a polymer/PCBM bulk heterojunction are directly resolved. Injection of holes into MDMO‐PPV is markedly delayed with respect to [60]PCBM excitation. The fastest component of the delayed response is attributed to the PCBM–polymer hole‐transfer process (30 ± 10 fs), while the slower component (～150 fs) is provisionally assigned to energy transfer and/or relaxation inside PCBM nanoclusters. The charge generation through the hole transfer is therefore as fast and efficient as through the electron‐transfer process. Exciton harvesting efficiency after PCBM excitation crucially depends on the concentration of the methanofullerene in the blend, which is related to changes in the blend morphology. Ultrafast charge generation is most efficient when the characteristic scale of phase separation in the blend does not exceed ～20 nm. At larger‐scale phase separation, the exciton harvesting dramatically declines. The obtained results on the time scales of the ultrafast charge generation after PCBM excitation and their dependence on blend composition and morphology are instrumental for the future design of fullerene‐derivative‐based photovoltaic devices.