Performance Of Organic Photovoltaic Devices Research Articles

Enhancing the indoor performance of organic photovoltaic devices: interface engineering with an aminobenzoic-acid-based self-assembled monolayer

Significant advances in the performance of organic photovoltaic (OPV) devices can facilitate their use in internet of things applications. However, achieving excellent photostability and high efficiency using stable, efficient OPV devices in indoor settings is considerably difficult. To address this issue, a zinc oxide (ZnO) electron transport layer (ETL) was modified with a self-assembled monolayer of 4-aminobenzoic acid (ABA) in the present study, and the impact of this modification was correlated with the indoor performance of an OPV device with the PM6:L8-BO photoactive layer. The ABA-treated ZnO ETL exhibited a significant reduction in the work function (from 4.51 to 4.04 eV), surface roughness (from 0.201 to 0.177 nm), and hydrophilicity of an indium-tin-oxide electrode; this aided in selectively extracting charge carriers from the device and minimizing trap-assisted recombination losses. Additionally, the ABA treatment of the ZnO ETL considerably enhanced the electron mobility and recombination resistance. It reduced the trap density, thereby enabling the ZnO/ABA-based device to achieve improved performance. Consequently, the ZnO/ABA-based device exhibited a noteworthy 14.68% higher maximum power output than that of the device without any ZnO surface modification under 1000 lx halogen (HLG) illumination (P out, max = 354.48 and 309 µA cm−2, respectively). Moreover, under thermal illumination conditions (1000 lx HLG lighting), the ZnO/ABA-based device sustained ∼74% of its initial power conversion efficiency over 120 h, significantly higher than its ABA-free equivalent (∼55%).

THE OPTIMIZATION OF P3HT:PCBM THIN FILM THICKNESS FOR ORGANIC SOLAR CELLS

This study presents the complex relationship between film thickness and the properties of P3HT:PCBM thin films, looking at how different thicknesses affected their structural and optical properties. Poly(3, hexylthiophene) (P3HT) and poly(3, hexylthiophene) (PCMB) were blended in a 0.6:1 ratio and deposited using spin coating techniques. The research involve investigating the resulting changes in surface topography, optical properties, and electrical behaviour by systematically adjusting the film thickness through multiple coating repetitions ranging from one to three repetitions. Profilometric analysis revealed a direct relationship between film thickness and surface roughness, highlighting the importance of thickness in interfacial interactions within solar cells. Optical studies revealed fascinating trends in absorbance, transmittance, absorption coefficient, and extinction coefficient, highlighting the films' behaviour at various wavelengths. Surprisingly, regardless of thickness, the optical band gap remained constant, providing valuable insights for optimizing photon energy conversion. Measurements of the Hall effect revealed the effect of thickness on carrier mobility, concentration, conductivity, resistivity, and Hall voltage. Thinner films had higher mobility but lower carrier concentration, revealing a delicate balance critical for optimizing charge transport. The comprehensive analysis of the study sheds light on the complex interplay between film thickness and various properties, providing useful guidance for designing efficient P3HT:PCBM organic solar cells. This study's findings highlight the importance of precise control over film dimensions in improving the performance and efficiency of organic photovoltaic devices. This investigation paves the way for tailored approaches in the fabrication of next-generation organic solar cells, pushing the limits of renewable energy technology.

Improving Performance of Organic Photovoltaic Devices under Low Illuminations

Improving Performance of Organic Photovoltaic Devices under Low Illuminations

Theoretical study on organic photovoltaic heterojunction FTAZ/IDCIC

Understanding organic photovoltaic (OPV) work principles and the materials’ optoelectronic properties is fundamental for developing novel heterojunction materials with the aim of improving power conversion efficiency (PCE) of organic solar cells. Here, in order to understand the PCE performance (>13%) of OPV device composed of the non-fullerene acceptor fusing naphtho[1,2-b:5,6-b′]dithiophene with two thieno[3,2-b]thiophene (IDCIC) and the polymer donor fluorobenzotriazole (FTAZ), with the aid of extensive quantum chemistry calculations, we investigated the geometries, molecular orbitals, excitations, electrostatic potentials, transferred charges and charge transfer distances of FTAZ, IDCIC and their complexes with face-on configurations, which was constructed as heterojunction interface model. The results indicate that, the prominent OPV performance of FTAZ:IDCIC heterojunction is caused by co-planarity between the donor and acceptor fragments in IDCIC, the the charge transfer (CT) and hybrid excitations of FTAZ and IDCIC, the complementary optical absorptions in visible region, and the large electrostatic potential difference between FTAZ and IDCIC. The electronic structures and excitations of FTAZ/IDCIC complexes suggest that exciton dissociation can fulfill through the decay of local excitation exciton in acceptor by means of hole transfer, which is quite different from the OPVs based on fullerenes acceptor. The rates of exciton dissociation, charge recombination and CT processes, which were evaluated by Marcus theory, support the efficient exciton dissociation that is also responsible for good photovoltaic performance.

Compromising Charge Generation and Recombination of Organic Photovoltaics with Mixed Diluent Strategy for Certified 19.4% Efficiency.

The ternary blend is demonstrated as an effective strategy to promote the device performance of organic photovoltaics (OPVs) due to the dilution effect. While the compromise between the charge generation and recombination remains a challenge. Here, a mixed diluent strategy for further improving the device efficiency of OPV is proposed. Specifically, the high-performance OPV system with a polymer donor, i.e., PM6, and a nonfullerene acceptor (NFA), i.e., BTP-eC9, is diluted by the mixed diluents, which involve a high bandgap NFA of BTP-S17 and a low bandgap NFA of BTP-S16 (similar with that of the BTP-eC9). The BTP-S17 of better miscibility with BTP-eC9 can dramatically enhance the open-circuit voltage (VOC ), while the BTP-S16 maximizes the charge generation or the short-circuit current density (JSC ). The interplay of BTP-17 and BTP-S16 enables better compromise between charge generation and recombination, thus leading to a high device performance of 19.76% (certified 19.41%), which is the best among single-junction OPVs. Further analysis on carrier dynamics validates the efficacy of mixed diluents for balancing charge generation and recombination, which can be further attributed to the more diverse energetic landscapes and improved morphology. Therefore, this work provides an effective strategy for high-performance OPV for further commercialization.

Dithieno[3,2-a:2′,3′-c]phenazine based hole-transporting materials for efficient perovskite solar cells: Effects of donors numbers

Incorporation of electron-deficient polycyclic aromatics into molecular skeleton has been proved to be an effective strategy for improving the device performance of organic photovoltaics. In this context, three low-cost hole-transporting materials (HTMs) endowed with dithieno[3,2-a:2′,3′-c]phenazine core were successfully synthesized and employed for perovskite solar cells (PSCs). A comparative evaluation in relation to the numbers of peripheral donors was systematically investigated by measurement of their photophysical, electrochemical and photovoltaic performance. It is revealed that the low-symmetrical WH04 featuring three triphenylamine (TPA) donors exhibited a deeper HOMO level, a higher hole-transporting capacity and smoother film morphology than the molecules with two or four terminal donors. As a result, the WH04-based PSCs realized the highest power conversion efficiency of 20.52%, accompanied with excellent long-term device stability, which is competitive with spiro-OMeTAD based devices. We believe that molecular engineering of donors numbers is envisioned as an effective strategy for constructing highly efficient D-A-D type HTMs for PSCs.

Effects of stirring temperature of P3HT:PCBM solution on device performance of organic photovoltaics

Effects of stirring temperature of P3HT:PCBM solution on device performance of organic photovoltaics

Systematic Investigation of Core and Endcap Selection on the Development of Functional π-Conjugated Materials

We investigate the optoelectronic properties of four new π-conjugated materials, which feature either a 3,4-ethylenedioxythiophene (EDOT) or an EDOT-flanked benzothiadiazole aryl core with two N-annulated perylene diimide (NPDI) or theobromine endcaps. Endcap selection was an important factor for the preferred molecular geometry, where the use of NPDI endcaps induced a dragonfly-type conformation and the use of theobromine endcaps promoted a corkscrew-like conformation. Electrochemically, the choice of aryl π-conjugated core was found to have a strong influence on the molecule’s highest occupied molecular orbital (HOMO) energy level, while the choice of endcap had a more profound effect on the lowest unoccupied molecular orbital (LUMO) energy level. Although the optical absorption profiles were generally dominated by endcap contributions, using the larger EDOT-flanked benzothiadiazole aryl core was found to decrease the optical energy band gap. Proof-of-concept organic photovoltaic (OPV) devices, using a PM6:Y6 bulk heterojunction (BHJ) photoactive layer, were fabricated using the four new π-conjugated materials as the cathode interlayer (CIL). The molecules featuring the EDOT aryl core (A and B) enabled OPV device power conversion efficiencies (PCEs) by around 12%, comparable to control devices using PDINN as the CIL, while those featuring the EDOT-flanked benzothiadiazole aryl core (C and D) obtained PCEs of 10.5%. The observed differences in OPV device performance were attributed to superior solubility and subsequent CIL film formation in the case of A and B, compared to C and D, which, in turn, led to improved contact between the Ag top electrode and the BHJ photoactive layer.

Thermal Activation of PEDOT:PSS/PM6:Y7 Based Films Leads to Unprecedent High Short‐Circuit Current Density in Nonfullerene Organic Photovoltaics

AbstractFinding an effective approach to suppress trap formation is a potential route for enhancing the performance of nonfullerene organic photovoltaic (NF‐OPVs) devices. Here, an extraordinary short‐circuit current density (JSC) value of 32.65 mA cm‐2 is achieved, higher than the state‐of‐the art NF‐OPVs reported, reaching a high power conversion efficiency (PCE) of 17.92%. This remarkable enhancement is exhibited through the fine‐tuning of PEDOT:PSS/PM6:Y7 films and interface morphologies via applying the prethermal treatment approach (Pre‐TT) to the devices, which exhibit JSC and PCE enhancement of 21% and 8%, respectively, compared to the pristine devices. Accordingly, the dependence of the JSC upon the Pre‐TT approach through a range of morphological, optical, electrical, and advanced transient measurements is investigated. The Pre‐TT‐based films are found to possess optimal smooth blend morphology with better dispersity owing to reduced domain size. Moreover, the measurements show that the optimized treated devices present higher exciton dissociation probabilities and generation rate of the free charge carriers, showing an ideal balanced electron/hole mobility that reveals the JSC and PCE enhancement. Hence, Pre‐TT approach provides a facile passivation strategy that reduces the trap state density of the blend film, improves interface charge transfer, allows balanced electron/hole mobility, and thus promotes device performance.

Impact of the bilayer electron transport layer in the donor acceptor bulk heterojunctions for improved inverted organic photovoltaic performance

Functionalization at interface of the electron transport layer and the organic polymeric donor and non-fullerene acceptor bulk heterojunction layer in photovoltaic devices that have an inverted structure, is a unique strategy for improving performance. Here we demonstrate improved interfacial nanomorphology of the well-known PTB7-Th donor and IEICO-4F acceptor bulk heterojunction (BHJ) on an atomic layer deposited (ALD) ultrathin titanium oxide (TiO2) passivated sol–gel grown zinc oxide (ZnO) electron transport bilayer and highlight how this is correlated to the overall organic photovoltaic device performance. Synchrotron-based grazing incidence wide-angle X-ray scattering (GIWAXS) has been used to demonstrate an enhanced face-on conformation within the BHJ with highly crystalline ZnO/TiO2/BHJ layers and this is greatest for the very thinnest of TiO2 layers on ZnO (ZnT1), from just two deposition cycles, relative to both four (ZnT2) and eight (ZnT3) cycles. Photovoltaic devices with BHJs grown over ZnT1, showed an overall average increase of 30.3 ± 0.5 % in the power conversion efficiency (PCE 10.3 ± 0.5 %), a 14.3 ± 1 % increase in the fill-factor, FF (60.1 ± 1 %), 2.9 ± 0.05 % improvement in Voc (0.70 ± 0.05 mV) and 13.6 ± 0.5 % higher JSc (24.2 ± 0.5 mA/cm2), compared to the control device,with a best efficiency of 11.1 ± 0.5 % PCE, 61.9 ± 1 % FF, 0.70 ± 0.5 mV Voc and 25.0 ± 0.5 mA/cm2Jsc. We conclude that the molecular crystal conformation of the organic donor acceptor BHJ layer can be partly controlled through the ETL along with an enhanced organic inorganic interface which strongly influences the OPV performance.

Light intensity dependence of the photocurrent in organic photovoltaic devices

The competition between recombination and extraction of carriers defines the charge collection efficiency and, therefore, the overall performance of organic photovoltaic devices, including solar cells and photodetectors. In this work, we describe different components of the steady-state light intensity-dependent photocurrent (IPC) and charge collection efficiency under operational conditions. Further, we demonstrate how different loss mechanisms can be identified based on their unique signatures in the IPC. In particular, we show how IPC can be used to distinguish first-order, trap-assisted recombination from other first-order photocurrent loss mechanisms, which dominate at the low-intensity characteristic of indoor light-harvesting applications. The theoretical framework is presented and verified by a one-dimensional drift-diffusion device model. Finally, the extended IPC methodology is validated on organic thin-film photovoltaic devices. We conclude that the relatively straightforward measurement of IPC over a large dynamic range can be a powerful tool for understanding solar and indoor device fundamentals. • IPC is a tool for understanding photovoltaic device fundamentals • Photocurrent loss mechanisms are identified based on their signatures in IPC • The theoretical framework is verified with a drift-diffusion device model • Experimental demonstration of IPC method on state-of-the-art organic solar cells Zeiske et al. present a combined theoretical and experimental study of intensity-dependent photocurrent (IPC), a tool for understanding solar and indoor device fundamentals, to identify different photovoltaic device performance-limiting photocurrent loss mechanisms based on their unique signatures in IPC.

Understanding interfacial energy structures in organic solar cells using photoelectron spectroscopy: A review

Organic solar cells (OSCs) have received considerable attention as a promising clean energy-generating technology because of their low cost and great potential for large-scale commercial manufacturing. With significant advances in new charge-transport material design, interfacial engineering, and their operating conditions, power conversion efficiencies of OSCs have continued to increase. However, a fundamental understanding of charge carrier transport and especially how ionic moieties affect carrier transport is still lacking in OSCs. In this regard, photoelectron spectroscopy has provided valuable information about interfacial electronic structures. The interfacial electronic structure of OSC interlayers greatly impacts charge extraction and recombination, controls energy level alignment, guides active layer morphology, improves material’s compatibility, and plays a critical role in the resulting power conversion efficiency of OSCs. Interfacial engineering incorporating inorganic, organic, and hybrid materials can effectively enhance the performance of organic photovoltaic devices by reducing energy barriers for charge transport and injection while improving compatibility between metal oxides and donor–acceptor based active layers or transparent conducting electrodes. This article provides a review of recent developments in interfacial engineering underlying organic photovoltaic devices of donor–acceptor interfaces.

Submolecular Resolution Imaging of P3HT:PCBM Nanostructured Films by Atomic Force Microscopy: Implications for Organic Solar Cells.

The efficiency of organic bulk-heterojunction (BHJ) solar cells depends greatly on both the bulk and surface structure of the nanostructured bicontinuous interpenetrating network of materials, known as the active layer. The morphology of the top layer of a coated film is often resolved at the scale of a few nanometers, but fine details of the domains and the order within them are more difficult to identify. Here, we report a high-resolution atomic force microscopy (AFM) investigation of various stoichiometries of the well-studied poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester (P3HT:PCBM) active layer mixture. Images of the surface were obtained using AC-mode AFM exciting higher-order resonance frequencies of a standard silicon probe, a promising technique for acquiring real-space images of organic-based thin films with nanoscale and even submolecular resolution. We provide firm evidence of the nanoscale organization of the P3HT polymer and of the P3HT:PCBM stoichiometric mixtures at the surface-air interface of the BHJ architecture. Our study shows the characteristic periodicity of the regioregular P3HT identified in the nanoscale domain areas with submolecular resolution. Such areas are then distorted in place when adding different quantities of PCBM forming stoichiometric mixtures. When the samples were exposed to ambient light, the morphologies were very different, and submolecular resolution was not achieved. This approach is shown to provide a precise view of the active layer's nanostructure and will be useful for studies of other materials as a function of various parameters, with particular attention to the role of the acceptor in tuning morphology for understanding optimum performance in organic photovoltaic devices.

Ultrafast charge generation in a homogenous polymer domain

Efficient charge generation contributes greatly to the high performance of organic photovoltaic devices. The mechanism of charge separation induced by heterojunction has been widely accepted. However, how and why free charge carriers can generate in homogenous polymer domains remains to be explored. In this work, the extended tight-binding SSH model, combined with the non-adiabatic molecular dynamics simulation, is used to construct the model of a polymer array in an applied electric field and simulate the evolution of an excited state. It is found that under a very weak external electric field 5.0 × 10−3 V/Å, the excited state can evolve directly into spatially separated free charges at the femtosecond scale, and the efficiency is up to 97%. The stacking structure of the polymer array leads to intermolecular electron mutualization and forms intermolecular coupling. This interaction tends to delocalize the excited states in organic semiconductors, competing with the localization caused by electron–phonon coupling. Excitons within the homogenous polymer domains have lower binding energy, less energy dissipation, and ultrafast charge separation. Therefore, the initial excited state can evolve directly into free carriers under a very weak electric field. This finding provides a reasonable explanation for ultrafast charge generation in pure polymer phases and is consistent with the fact that delocalization always coexists with ultrafast charge generation. Moreover, the devices based on homogenous polymer domains are supposed to be stress-sensitive and performance-anisotropic since the above two interactions have contrary effects and work in perpendicular directions. This work is expected to bring inspiration for the design of organic functional materials and devices.

Highly efficient flexible organic photovoltaic modules for sustainable energy harvesting under low-light condition via suppressing voltage-drop by metal-mediated cross-linkable polymer interfacial layer

This study aims to expand the practical applications of large-area flexible organic photovoltaics (OPV), such that they retain their high stability and efficiency even under various weather conditions and external stresses. By developing polyethyleneimine derivative-based cathode interfacial layer (CIL) and non-fullerene acceptor (NFA) material in OPVs, the efficiency and stability decrease rapidly due to an undesirable interaction when these two materials are concomitantly applied. In this study, we designed a novel low-cost metal-mediated cross-linked non-conjugated polymer interfacial layer (c-PEIE) and improved the device performance and stability of flexible OPVs from the cell-to-module scale. c-PEIE CIL based flexible OPV cell achieves one of the highest power conversion efficiencies (PCE) of 16.45% and remarkable photostability, retaining 77.58% of its initial PCE for 110 h under continuous light illumination, while the conventional PEIE based cells realize a PCE of 12.58% and poor device stability. Accordingly, a 50 cm2, large-area, flexible OPV module was also fabricated with an excellent PCE of 13.12% which is ∼ 80% as efficient as small-area flexible cells. Notably, c-PEIE based OPV devices maintain high output power on cloudy days, which is a particular point of interest to efficiently harvest sunlight energy constantly. The tunable energy barrier and significant low-leakage current of CIL play a critical role in reducing open-circuit voltage and fill factor losses under low-light environments. Such energy sources can provide power efficiently all day long in low-light or cloudy environments to the Internet of Things wireless networks integrated with battery-independent photovoltaics.

One-Pot Synthesis of Fully Conjugated Amphiphilic Block Copolymers Using Asymmetrically Functionalized Push–Pull Monomers

Developing a fully conjugated block copolymer with a specific molecular weight and block ratio is crucial for understanding the impact of the bulk heterojunction morphology on device performance in organic photovoltaic devices. Herein, we have revealed a strategy to synthesize fully conjugated amphiphilic diblock copolymers in one pot by combining Suzuki and Stille pseudoliving polymerizations. Our strategy was to synthesize asymmetrically functionalized push–pull monomers as precursors for the synthesis of the donor polymer poly[4,8-bis(5-(2-ethylhexyl)-4-hexylthiophene-2-yl)-benzo[1,2-b:4,5b′]dithiophenebenzo [c][1,2,5]thiadiazole] p(BDT-BT) and the acceptor polymer poly[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene) p(NDI-TT). The acceptor monomer (M1) was synthesized with tributyltin and triflate functionalities, whereas the donor monomer (M2) was prepared with MIDA boronate and bromide groups. These heterobifunctional acceptor and donor monomers were suitable for Stille and Suzuki polymerizations, respectively. Initially, TfOPh-p(NDI-TT) was synthesized by pseudoliving Stille polymerization with a single triflate (OTf) end group and specific molecular weight. Subsequently, TfOPh-p(NDI-TT) was used as a macroinitiator to grow an amphiphilic diblock copolymer (BCP1) via a grafting-into approach, where the donor polymer block was grown using pseudoliving Suzuki polymerization. Lastly, one-pot synthesis of the amphiphilic diblock copolymer (BCP2) was established using optimized conditions developed for stepwise block copolymer synthesis.

Random copolymers with different Cl position for optimizing morphology with acceptor

We prepared a series of D-A-D’ type random copolymers, which are based on PBDB-S-3Cl and PBDB-S-4Cl, PBDB-S-CO-3Cl–4Cl (1:9), PBDB-S-CO-3Cl–4Cl (3:7), PBDB-S-CO-3Cl–4Cl (7:3) and PBDB-S-CO-3Cl–4Cl (9:1) with 3-chloro or 4-chloro and 2-s-alkylated thiophene on benzodithiophene (BDT), to examine the position effects of chlorine substitution of PBDB-S on its photovoltaic performance in organic photovoltaics (OPVs). The modulation of composition of random copolymer with the position effects of chlorine substitution affect the performance of organic photovoltaic (OPV) devices. The PBDB-S-CO-3Cl–4Cl (9:1) random copolymer-based OPV devices exhibit the highest power conversion efficiency (PCE) of 13.31%, and fill factor (FF) of 0.63, which was higher performance than those of homopolymer PBDB-S-3Cl and PBDB-S-4Cl.

Surfactant Engineering and Its Role in Determining the Performance of Nanoparticulate Organic Photovoltaic Devices

The fabrication of organic photovoltaics (OPVs) from non-hazardous nanoparticulate (NP) inks offers considerable promise for the development of eco-friendly large-scale printed solar modules. However, the typical NP core–shell morphology (driven by the different donor/acceptor affinities for the surfactant used in NP synthesis) currently hinders the photovoltaic performance. As such, surfactant engineering offers an elegant approach to synthesizing a more optimal intermixed NP morphology and hence an improved photovoltaic performance. In this work, the morphology of conventional sodium dodecyl sulfate (SDS) and 2-(3-thienyl) ethyloxybutylsulfonate (TEBS)-stabilized poly(3-hexylthiophene) (P3HT) donor:phenyl-C61-butyric acid methyl ester (PC61BM) acceptor NPs is probed using scanning transmission X-ray microscopy, UV–vis spectroscopy, grazing-incidence X-ray diffraction, and scanning electron microscopy. While the SDS-stabilized NPs exhibit a size-independent core–shell morphology, this work reveals that TEBS-stabilized NPs deliver an intermixed morphology, the extent of which depends on the particle size. Consequently, by optimizing the TEBS-stabilized NP size and distribution, NP-OPV devices with a power conversion efficiency that is ∼50% higher on average than that of the corresponding SDS-based NP-OPV devices are produced.

Gold(III) Porphyrin Was Used as an Electron Acceptor for Efficient Organic Solar Cells.

The widespread use of nonfullerene-based electron-accepting materials has triggered a rapid increase in the performance of organic photovoltaic devices. However, the number of efficient acceptor compounds available is rather limited, which hinders the discovery of new, high-performing donor:acceptor combinations. Here, we present a new, efficient electron-accepting compound based on a hitherto unexplored family of well-known molecules: gold porphyrins. The electronic properties of our electron-accepting gold porphyrin, named VC10, were studied by UV–Vis spectroscopy and by cyclic voltammetry (CV) , revealing two intense optical absorption bands at 500–600 and 700–920 nm and an optical bandgap of 1.39 eV. Blending VC10 with PTB7-Th, a donor polymer, which gives rise to an absorption band at 550–780 nm complementary to that of VC10, enables the fabrication of organic solar cells (OSCs) featuring a power conversion efficiency of 9.24% and an energy loss of 0.52 eV. Hence, this work establishes a new approach in the search for efficient acceptor molecules for solar cells and new guidelines for future photovoltaic material design.

Single‐Walled Carbon Nanotubes as an Additive in Organic Photovoltaics: Effects on Carrier Generation and Recombination Dynamics

Employing single‐walled carbon nanotubes (SWNTs) as an additive in the active layer of organic photovoltaics (OPV) to improve charge extraction is gaining weight in the research community. While SWNTs can transport charge carriers orders of magnitudes faster than conventional polymers, they also quench excitons and trap‐free charges, reducing device performance. Such influences of SWNTs on OPV device performance remain inadequately explored and incompletely understood. Herein, the impact of SWNTs, enriched in (6,5) chirality, on the charge generation and extraction properties of two different OPV devices is studied by femtosecond‐microsecond transient absorption spectroscopy and transient photovoltage/photocurrent techniques. It is shown that depending on the donor material properties (e.g., energetics), SWNTs can reduce carrier generation by quenching the excitons and increase carrier recombination through trapping processes. Then, by performing an analytical calculation of the current–voltage characteristics of the devices using the parameters determined via the transient measurements, it is shown that the increased recombination also relates to morphological changes induced by the SWNTs. These results shed light on the performance limiting factors of the SWNTs when incorporated into the active layer of the solar cells. This work thus can accelerate the blend optimization process for high‐performance organic solar cells.