Fullerene Blends Research Articles

Utilizing Forster resonance energy transfer to extend spectral response of PCDTBT:PCBM solar cells

Light harvesting in the near-infrared part of the solar spectrum is important to achieve high efficiency polymer solar cells (PSCs). In this work, we demonstrate that we take an existing polymer:fullerene blend and extend its spectral response into the near-IR region by adding a small amount near-IR absorbing dye in the blend. The polymer studied in this work is Poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT). By adding only 2.5% squaraine dye to the blend, we were able to extend the spectral response of the resulting devices 100 nm into the near-IR spectral region. We show that the enhanced light harvesting is due to efficient Forster resonance energy transfer (FRET) between PCDTBT and the squaraine dye, resulting in an increase in power conversion efficiency. This type of ternary polymer solar cells is unique in that it allows the use of a small amount of selected dyes to extend light harvesting in infrared region.

Revelation of Interfacial Energetics in Organic Multiheterojunctions.

Efficient charge generation via exciton dissociation in organic bulk heterojunctions necessitates donor–acceptor interfaces, e.g., between a conjugated polymer and a fullerene derivative. Furthermore, aggregation and corresponding structural order of polymer and fullerene domains result in energetic relaxations of molecular energy levels toward smaller energy gaps as compared to the situation for amorphous phases existing in homogeneously intermixed polymer:fullerene blends. Here it is shown that these molecular energy level shifts are reflected in interfacial charge transfer (CT) transitions and depending on the existence of disordered or ordered interfacial domains. It can be done so by systematically controlling the order at the donor–acceptor interface via ternary blending of semicrystalline and amorphous model polymers with a fullerene acceptor. These variations in interfacial domain order are probed with luminescence spectroscopy, yielding various transition energies due to activation of different recombination channels at the interface. Finally, it is shown that via this analysis the energy landscape at the organic heterojunction interface can be obtained.

Tin-Free Direct C-H Arylation Polymerization for High Photovoltaic Efficiency Conjugated Copolymers.

A new and highly regioselective direct C-H arylation polymerization (DARP) methodology enables the reproducible and sustainable synthesis of high-performance π-conjugated photovoltaic copolymers. Unlike traditional Stille polycondensation methods for producing photovoltaic copolymers, this DARP protocol eliminates the need for environmentally harmful, toxic organotin compounds. This DARP protocol employs low loadings of commercially available catalyst components, Pd2(dba)3·CHCl3 (0.5 mol%) and P(2-MeOPh)3 (2 mol%), sterically tuned carboxylic acid additives, and an environmentally friendly solvent, 2-methyltetrahydrofuran. Using this DARP protocol, several representative copolymers are synthesized in excellent yields and high molecular masses. The DARP-derived copolymers are benchmarked versus Stille-derived counterparts by close comparison of optical, NMR spectroscopic, and electrochemical properties, all of which indicate great chemical similarity and no significant detectable structural defects in the DARP copolymers. The DARP- and Stille-derived copolymer and fullerene blend microstructural properties and morphologies are characterized with AFM, TEM, and XRD and are found to be virtually indistinguishable. Likewise, the charge generation, recombination, and transport characteristics of the fullerene blend films are found to be identical. For the first time, polymer solar cells fabricated using DARP-derived copolymers exhibit solar cell performances rivalling or exceeding those achieved with Stille-derived materials. For the DARP copolymer PBDTT-FTTE, the power conversion efficiency of 8.4% is a record for a DARP copolymer.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV–vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy.

Carbon Dangling Bonds in Photodegraded Polymer:Fullerene Solar Cells

Intrinsic photodegradation of organic solar cells, theoretically attributed to CH bond rearrangement/breaking, remains a key commercialization barrier. This work presents, via dark electron paramagnetic resonance (EPR), the first experimental evidence for metastable C dangling bonds (DBs) formed by blue/UV irradiation of polymer:fullerene blend films in nitrogen. The DB density increases with irradiation and decreases ≈4‐fold after 2 weeks in the dark. The dark EPR also shows increased densities of other spin‐active sites in photodegraded polymer, fullerene, and polymer:fullerene blend films, consistent with broad electronic measurements of fundamental properties, including defect/gap state densities. The EPR and electronic measurements enable identification of defect states, whether in the polymer, fullerene, or at the donor/acceptor (D/A) interface. Importantly, the EPR results indicate that the DBs are at the D/A interface, as they were present only in the blend films. The role of polarons in interface DB formation is also discussed.

Ultrafast Charge Transfer and Enhanced Absorption in MoS2-Organic van der Waals Heterojunctions Using Plasmonic Metasurfaces.

Hybrid organic-inorganic heterostructures are attracting tremendous attention for optoelectronic applications due to their low-cost processing and high performance in devices. In particular, van der Waals p-n heterojunctions formed between inorganic two-dimensional (2D) materials and organic semiconductors are of interest due to the quantum confinement effects of 2D materials and the synthetic control of the physical properties of organic semiconductors, enabling a high degree of tunable optoelectronic properties for the heterostructure. However, for photovoltaic applications, hybrid 2D-organic heterojunctions have demonstrated low power conversion efficiencies due to the limited absorption from constraints on the physical thickness of each layer. Here, we investigate the ultrafast charge transfer dynamics between an organic polymer:fullerene blend and 2D n-type MoS2 using transient pump-probe reflectometry. We employ plasmonic metasurfaces to enhance the absorption and charge photogeneration within the physically thin hybrid MoS2-organic heterojunction. For the hybrid MoS2-organic heterojunction in the presence of the plasmonic metasurface, the charge generation within the polymer is enhanced 6-fold, and the total active layer absorption bandwidth is increased by 90 nm relative to the polymer:fullerene blend alone. We demonstrate that MoS2-organic heterojunctions can serve as hybrid solar cells, and their efficiencies can be improved using plasmonic metasurfaces.

Bulk heterojunction morphology of polymer:fullerene blends revealed by ultrafast spectroscopy.

Morphology of organic photovoltaic bulk heterojunctions (BHJs) – a nanoscale texture of the donor and acceptor phases – is one of the key factors influencing efficiency of organic solar cells. Detailed knowledge of the morphology is hampered by the fact that it is notoriously difficult to investigate by microscopic methods. Here we all-optically track the exciton harvesting dynamics in the fullerene acceptor phase from which subdivision of the fullerene domain sizes into the mixed phase (2–15 nm) and large (>50 nm) domains is readily obtained via the Monte-Carlo simulations. These results were independently confirmed by a combination of X-ray scattering, electron and atomic-force microscopies, and time-resolved photoluminescence spectroscopy. In the large domains, the excitons are lost due to the high energy disorder while in the ordered materials the excitons are harvested with high efficiency even from the domains as large as 100 nm due to the absence of low-energy traps. Therefore, optimizing of blend nanomorphology together with increasing the material order are deemed as winning strategies in the exciton harvesting optimization.

Novel organic photovoltaic polymer blends: A rapid, 3-dimensional morphology analysis using backscattered electron imaging in the scanning electron microscope

Finding the optimal morphology of novel organic photovoltaic (OPV) polymer blends is a major obstacle slowing the development of more efficient OPV devices. With a focus on accelerating the systematic morphology optimisation process, we demonstrate a technique offering rapid high-resolution, 3-dimensional blend morphology analysis in the scanning electron microscope. This backscattered electron imaging technique is used to investigate the morphological features and length-scales defining the promising PffBT4T-2OD:PC70BM blend system and show how its photovoltaic performance is related to the nature of its phase separation. Low-voltage backscattered electron imaging can be used to probe for structure and domain stacking through the thickness of the film, as well as imaging surface morphology with highly competitive spatial resolution. For reference, we compare our results with equivalent images of the widely studied P3HT:PC60BM blend system. Our results also demonstrate that backscattered electron imaging offers significant advantages over conventional cross-sectional imaging techniques, and show that it enables a fast, systematic approach to control 3-dimensional active layer morphology in polymer:fullerene blends.

Ionizing radiation exposure reveals instability of purified domains in polymer/fullerene solar cells

Solar cells based on conjugated polymer and fullerene blends exhibit morphology-dependent stability towards ionizing radiation exposure. Blend thin film solar cells of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C60-butyric acid methyl ester (PCBM) were irradiated up to 1Mrad with X-rays (10–60KeV) and investigated with resonance Raman and photocurrent/photovoltage modulation spectroscopy and imaging. Bulk blend morphological characteristics were pre-selected by controlling film processing conditions (i.e., solvent and thermal annealing). As-cast P3HT/PCBM devices with a large fraction of a well-mixed phase display improvements in performance upon application of post-irradiation annealing treatments. On the other hand, devices annealed prior to irradiation showed irreversible performance degradation that could not be recovered following annealing treatments after exposure. Resonance Raman spectroscopy and imaging following irradiation up to 1Mrad reveals virtually no changes in the P3HT structural and packing integrity for both types of devices. Intensity modulated photocurrent/photovoltage spectroscopy measurements indicate that radiation-induced performance degradation is concentrated in the vicinity of device contacts, evident from large alterations in charge extraction kinetics. We propose that charge transfer from the aluminum cathode leads to formation of a space charge zone which becomes more pronounced in devices with greater phase purification (i.e., larger PCBM crystallites in the vicinity of the cathode). Importantly, well-mixed P3HT/PCBM regions, which are more plentiful in as-cast devices, appear to mitigate radiation-induced performance degradation since application of post-irradiation annealing treatments restores device performances to pristine levels. Our results suggest that greater morphological stability, such as polymer/fullerene systems forming co-crystals, is key for suppressing performance losses from ionizing radiation exposure.

The fate of electron-hole pairs in polymer:fullerene blends for organic photovoltaics.

There has been long-standing debate on how free charges are generated in donor:acceptor blends that are used in organic solar cells, and which are generally comprised of a complex phase morphology, where intermixed and neat phases of the donor and acceptor material co-exist. Here we resolve this question, basing our conclusions on Stark effect spectroscopy data obtained in the absence and presence of externally applied electric fields. Reconciling opposing views found in literature, we unambiguously demonstrate that the fate of photogenerated electron–hole pairs—whether they will dissociate to free charges or geminately recombine—is determined at ultrafast times, despite the fact that their actual spatial separation can be much slower. Our insights are important to further develop rational approaches towards material design and processing of organic solar cells, assisting to realize their purported promise as lead-free, third-generation energy technology that can reach efficiencies over 10%.

Electron Transport Layer-Free Solar Cells Based on Perovskite-Fullerene Blend Films with Enhanced Performance and Stability.

The solution processing of pinhole-free methylammonium lead triiodide perovskite-C70 fullerene (MAPbI3 :C70 ) blend films on fluorine-doped tin oxide (FTO)-coated glass substrates is presented. Based on this approach, a simplified and robust protocol for the preparation of efficient electron-transport layer (ETL)-free perovskite solar cells is described. Power conversion efficiency (PCE) of 13.6 % under AM 1.5 G simulated sunlight is demonstrated for these devices. Comparative impedance spectroscopy and photostability analysis of the MAPbI3 :C70 and single MAPbI3 films compared with conventional compact TiO2 ETL-based devices are shown. The beneficial impact of using MAPbI3 :C70 blend films is emphasized.

Optically tuned poly (3-hexylthiophene-2,5-diyl) P3HT/PCBM (modified fullerene) blend for plastic solar cell

Optically tuned poly (3-hexylthiophene-2,5-diyl) P3HT/PCBM (modified fullerene) blend for plastic solar cell

Structure-Property Relations in Polymer:Fullerene Blends for Organic Solar Cells.

Organic solar cells consist of thin films combining an electron donor (often a conjugated polymer) with an electron acceptor (often a fullerene derivative), in a blend commonly referred to as bulk heterojunction material. Charge separation between the donor and the acceptor leads to the generation of carriers, which can be extracted from photovoltaic devices in the form of photocurrent. The generation mechanism of free, extractable charges has caused a lot of controversial discussion in literature. Our research has shown that all the steps involved in charge generation are strongly dependent on the arrangement of the donor and the acceptor (i.e. the structure) of the bulk heterojunction.

On the Effect of Prevalent Carbazole Homocoupling Defects on the Photovoltaic Performance of PCDTBT:PC71BM Solar Cells

The photophysical properties and solar cell performance of the classical donor–acceptor copolymer PCDTBT(poly(N‐9′‐heptadecanyl‐2,7‐carbazole‐alt ‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole))) in relation to unintentionally formed main chain defects are investigated. Carbazole–carbazole homocouplings (Cbz hc) are found to significant extent in PCDTBT made with a variety of Suzuki polycondensation conditions. Cbz hc vary between 0 and 8 mol% depending on the synthetic protocol used, and are quantified by detailed nuclear magnetic resonance spectroscopy including model compounds, which allows to establish a calibration curve from optical spectroscopy. The results are corroborated by extended time‐dependent density functional theory investigations on the structural, electronic, and optical properties of regularly alternating and homocoupled chains. The photovoltaic properties of PCDTBT:fullerene blend solar cells significantly depend on the Cbz hc content for constant molecular weight, whereby an increasing amount of Cbz hc leads to strongly decreased short circuit currents JSC. With increasing Cbz hc content, JSC decreases more strongly than the intensity of the low energy absorption band, suggesting that small losses in absorption cannot explain the decrease in JSC alone, rather than combined effects of a more localized LUMO level on the TBT unit and lower hole mobilities found in highly defective samples. Homocoupling‐free PCDTBT with optimized molecular weight yields the highest efficiency up to 7.2% without extensive optimization.

Low Open-Circuit Voltage Loss in Solution-Processed Small-Molecule Organic Solar Cells

We analyze the voltage losses at open circuit in solution-processed, small-molecule:fullerene blend solar cells, using electroluminescence and external quantum efficiency measurements and the reciprocity relationship between light absorption and emission. For solar cells made from oligo-thienylenevinylene-based donors and phenyl-C71 butyric acid methyl ester (PC71BM), we find that the voltage loss due to the finite breadth of the absorption edge is remarkably small, less than 0.01 eV in the best cases, while the voltage loss due to nonradiative recombination reaches 0.29 eV, one of the smallest values reported for an organic solar cell. As a result, the open-circuit voltage reaches around 1.0 V for an optical gap of 1.6 eV, greatly exceeding the voltage of a high-performance polymer-based system with similar optical gap. We assign the remarkably small absorption broadening loss to a low degree of energetic disorder in the small-molecule system that allows efficient charge separation at a lower driving for...

Dispersive Non-Geminate Recombination in an Amorphous Polymer:Fullerene Blend.

Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.

Improved efficiency of polymer-fullerene bulk heterojunction solar cells by the addition of Cu(II)-porphyrin-oligothiophene conjugates

Ternary organic photovoltaic devices were prepared through the addition of small amounts of metalloporphyin-terthiophenes to two established low bandgap polymer:fullerene blends. The methodology afforded a PCDTBT:PC71BM-based device that displayed an initial power conversion efficiency of 5.1%, an increase of 16% when compared to the binary blend. Among the range of metalloporphyrins considered in this study, the Cu(II)-porphyrin derivatives were found to result in the most significant efficiency improvements.

Enhancement of Photovoltaic Performance by Utilizing Readily Accessible Hole Transporting Layer of Vanadium(V) Oxide Hydrate in a Polymer-Fullerene Blend Solar Cell.

Herein, a successful application of V2O5·nH2O film as hole transporting layer (HTL) instead of PSS in polymer solar cells is demonstrated. The V2O5·nH2O layer was spin-coated from V2O5·nH2O sol made from melting-quenching sol-gel method by directly using vanadium oxide powder, which is readily accessible and cost-effective. V2O5·nH2O (n ≈ 1) HTL is found to have comparable work function and smooth surface to that of PSS. For the solar cell containing V2O5·nH2O HTL and the active layer of the blend of a novel polymer donor (PBDSe-DT2PyT) and the acceptor of PC71BM, the PCE was significantly improved to 5.87% with a 30% increase over 4.55% attained with PSS HTL. Incorporation of V2O5·nH2O as HTL in the polymer solar cell was found to enhance the crystallinity of the active layer, electron-blocking at the anode and the light-harvest in the wavelength range of 400-550 nm in the cell. V2O5·nH2O HTL improves the charge generation and collection and suppress the charge recombination within the PBDSe-DT2PyT:PC71BM solar cell, leading to a simultaneous enhancement in Voc, Jsc, and FF. The V2O5·nH2O HTL proposed in this work is envisioned to be of great potential to fabricate highly efficient PSCs with low-cost and massive production.

(Invited) The Effect of Increased Dielectric Screening on Bimolecular Recombination of Photogenerated Charges in Polymer:Fullerene Bulk Heterojunctions

Bimolecular recombination studies reveal a one order magnitude slower bimolecular recombination when normalized to charge mobility in a polymer:fullerene bulk heterojunction solar cell with a dielectric constant of seven. The techniques used were charge extraction using nanosecond switch combined with charge extraction by linearly increasing voltage and integral mode time of flight measurements. The measured high dielectric constant in the polymer:fullerene blend is due to the exceptionally high dielectric constant (16.7) of the conjugated polymer donor component employed. This value, indicative of increased dielectric screening of charges compared to most organic solar cell materials with a typical dielectric constant around 4,is one of the highest reported to date. The slower bimolecular recombination mentioned above is compared to well established poly(3-hexylthiophene) and low badngap polymer PCPDTBT:fullerene heterojunctions, and is explained by the smaller coulomb capture radius in a diffusion controlled recombination model. Longer charge carrier lifetimes together with a larger charge mobility in the high dielectric constant bulk heterojunctions leads to larger fill factors (0.6) and excellent photovoltaic performance in solar cells using large active layer thicknesses approaching 300 nm. Ultimately, increasing the dielectic constant of organic photoactive laterials to and beyond 10 is expected to bridge the performance gap between inorganic and organic solar cells.

Light‐Induced Degradation Mechanism in Poly(3‐hexylthiophene)/Fullerene Blend Solar Cells

The mechanism of light‐induced degradation in organic solar cells based on regioregular poly(3‐hexylthiophene) and indene‐C60 bisadduct is studied by transient absorption (TA) and electron spin resonance (ESR) measurements. After 45 h light exposure under simulated solar illumination at 100 mW cm−2, the short‐circuit current density, open‐circuit voltage, and fill factor are all degraded by about 20%–30% relative to the initial photovoltaic parameters. For the assignment of limiting conversion processes in the degraded solar cells, exciton diffusion into a donor/acceptor interface, charge transfer at the interface, charge dissociation into free charge carriers, and charge collection to each electrode are observed before and after the light exposure by the TA measurement. As a result, it is found that the charge collection deteriorates after the light exposure because of light‐induced charge trap formation in the bulk of the active layer. The origin of charge traps is further discussed on the basis of ESR measurements and density functional theory calculation.