25th anniversary article: Bulk heterojunction solar cells: understanding the mechanism of operation.
TL;DR: The status of understanding of the operation of bulk heterojunction (BHJ) solar cells is reviewed and a summary of the problems to be solved to achieve the predicted power conversion efficiencies of >20% for a single cell is concluded.
Abstract: The status of understanding of the operation of bulk heterojunction (BHJ) solar cells is reviewed. Because the carrier photoexcitation recombination lengths are typically 10 nm in these disordered materials, the length scale for self-assembly must be of order 10–20 nm. Experiments have verified the existence of the BHJ nanostructure, but the morphology remains complex and a limiting factor. Three steps are required for generation of electrical power: i) absorption of photons from the sun; ii) photoinduced charge separation and the generation of mobile carriers; iii) collection of electrons and holes at opposite electrodes. The ultrafast charge transfer process arises from fundamental quantum uncertainty; mobile carriers are directly generated (electrons in the acceptor domains and holes in the donor domains) by the ultrafast charge transfer (≈70%) with ≈30% generated by exciton diffusion to a charge separating heterojunction. Sweep-out of the mobile carriers by the internal field prior to recombination is essential for high performance. Bimolecular recombination dominates in materials where the donor and acceptor phases are pure. Impurities degrade performance by introducing Shockly–Read–Hall decay. The review concludes with a summary of the problems to be solved to achieve the predicted power conversion efficiencies of >20% for a single cell.
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2,219 citations
TL;DR: In this paper, the synergistic effects of a hydrocarbon solvent, a novel additive, a suitable choice of polymer side chain, and strong temperature-dependent aggregation of the donor polymer are used to produce active layers of organic solar cells in an environmentally friendly way.
Abstract: Organic solar cells have desirable properties, including low cost of materials, high-throughput roll-to-roll production, mechanical flexibility and light weight. However, all top-performance devices are at present processed using halogenated solvents, which are environmentally hazardous and would thus require expensive mitigation to contain the hazards. Attempts to process organic solar cells from non-halogenated solvents lead to inferior performance. Overcoming this hurdle, here we present a hydrocarbon-based processing system that is not only more environmentally friendly but also yields cells with power conversion efficiencies of up to 11.7%. Our processing system incorporates the synergistic effects of a hydrocarbon solvent, a novel additive, a suitable choice of polymer side chain, and strong temperature-dependent aggregation of the donor polymer. Our results not only demonstrate a method of producing active layers of organic solar cells in an environmentally friendly way, but also provide important scientific insights that will facilitate further improvement of the morphology and performance of organic solar cells. The processing of high-performance organic solar cells usually requires environmentally hazardous solvents. Now, hydrocarbon-based processing is shown to achieve relatively high performance in a more environmentally friendly way.
2,052 citations
TL;DR: Lewis reviews the status of solar thermal and solar fuels approaches for harnessing solar energy, as well as technology gaps for achieving cost-effective scalable deployment combined with storage technologies to provide reliable, dispatchable energy.
Abstract: Major developments, as well as remaining challenges and the associated research opportunities, are evaluated for three technologically distinct approaches to solar energy utilization: solar electricity, solar thermal, and solar fuels technologies. Much progress has been made, but research opportunities are still present for all approaches. Both evolutionary and revolutionary technology development, involving foundational research, applied research, learning by doing, demonstration projects, and deployment at scale will be needed to continue this technology-innovation ecosystem. Most of the approaches still offer the potential to provide much higher efficiencies, much lower costs, improved scalability, and new functionality, relative to the embodiments of solar energy-conversion systems that have been developed to date.
1,416 citations
TL;DR: In this article, the authors highlight recent progress on single-junction and tandem NFA solar cells and research directions to achieve even higher efficiencies of 15-20% using NFA-based organic photovoltaics are also proposed.
Abstract: Over the past three years, a particularly exciting and active area of research within the field of organic photovoltaics has been the use of non-fullerene acceptors (NFAs). Compared with fullerene acceptors, NFAs possess significant advantages including tunability of bandgaps, energy levels, planarity and crystallinity. To date, NFA solar cells have not only achieved impressive power conversion efficiencies of ~13–14%, but have also shown excellent stability compared with traditional fullerene acceptor solar cells. This Review highlights recent progress on single-junction and tandem NFA solar cells and research directions to achieve even higher efficiencies of 15–20% using NFA-based organic photovoltaics are also proposed.
1,404 citations
Cites background from "25th anniversary article: Bulk hete..."
...b, The operating mechanism of OPVs: (1) absorption of photons and creation of excitons; (2) diffusion of excitons to D/A interfaces; (3) dissociation of excitons to free charge carriers (holes and electrons) at D/A interfaces; (4) transportation of the charge carriers to electrodes; (5) extraction of the charge carriers at the electrodes....
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...7 V); and (3) Δ V3 (Δ VOC, nr) is due to the non-radiative recombination—this loss in organic solar cells (approximately 0....
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...(3) Setting up the relationships between the molecular structures of NFAs and small VOC loss....
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...1b: (1) absorption of photons and creation of excitons; (2) diffusion of excitons to D/A interfaces; (3) dissociation of excitons to free charge carriers (holes and electrons) at D/A interfaces; (4) transportation of the charge carriers to electrodes; and (5) extraction of the charge carriers at electrodes....
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...Considering the advantages of NFAs compared with fullerene acceptors, the combination of NFAs and the tandem concept shows great potential for very high performance OPVs: (1) NFAs have easily tunable bandgaps that can broaden the absorption in the NIR region for the rear cell or narrow the absorption to the blue region for the front cell; (2) small VOC loss of NFA sub-cells guarantees small VOC loss of tandem NFA solar cells; (3) the improved thermal stability of the NFA sub-cell is potentially advantageous for maintaining the performance of the front cell, which is usually challenging as a result of the unavoidable thermal treatments of the ICL....
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TL;DR: Progress is summarized, aiming to describe the molecular design strategy, to provide insight into the structure-property relationship, and to highlight the challenges the field is facing, with emphasis placed on most recent nonfullerene acceptors that demonstrated top-of-the-line photovoltaic performances.
Abstract: The bulk-heterojunction blend of an electron donor and an electron acceptor material is the key component in a solution-processed organic photovoltaic device. In the past decades, a p-type conjugated polymer and an n-type fullerene derivative have been the most commonly used electron donor and electron acceptor, respectively. While most advances of the device performance come from the design of new polymer donors, fullerene derivatives have almost been exclusively used as electron acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials, particularly small molecules and oligomers, have emerged as a promising alternative to replace fullerene derivatives. Compared to fullerenes, these new acceptors are generally synthesized from diversified, low-cost routes based on building block materials with extraordinary chemical, thermal, and photostability. The facile functionalization of these molecules affords excellent tunability to their optoelectronic and electrochemical properties. Within t...
1,269 citations
References
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TL;DR: In this paper, the carrier collection efficiency and energy conversion efficiency of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives.
Abstract: The carrier collection efficiency (ηc) and energy conversion efficiency (ηe) of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives. Composite films of poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) and fullerenes exhibit ηc of about 29 percent of electrons per photon and ηe of about 2.9 percent, efficiencies that are better by more than two orders of magnitude than those that have been achieved with devices made with pure MEH-PPV. The efficient charge separation results from photoinduced electron transfer from the MEH-PPV (as donor) to C60 (as acceptor); the high collection efficiency results from a bicontinuous network of internal donor-acceptor heterojunctions.
9,611 citations
TL;DR: In this article, the statistics of the recombination of holes and electrons in semiconductors were analyzed on the basis of a model in which the recombinations occurred through the mechanism of trapping.
Abstract: The statistics of the recombination of holes and electrons in semiconductors is analyzed on the basis of a model in which the recombination occurs through the mechanism of trapping. A trap is assumed to have an energy level in the energy gap so that its charge may have either of two values differing by one electronic charge. The dependence of lifetime of injected carriers upon initial conductivity and upon injected carrier density is discussed.
5,442 citations
TL;DR: In this article, the authors presented a review of several organic photovoltaics (OPV) technologies, including conjugated polymers with high-electron-affinity molecules like C60 (as in the bulk-heterojunction solar cell).
Abstract: There has been an intensive search for cost-effective photovoltaics since the development of the first solar cells in the 1950s. [1–3] Among all alternative technologies to silicon-based pn-junction solar cells, organic solar cells could lead the most significant cost reduction. [4] The field of organic photovoltaics (OPVs) comprises organic/inorganic nanostructures like dyesensitized solar cells, multilayers of small organic molecules, and phase-separated mixtures of organic materials (the bulkheterojunction solar cell). A review of several OPV technologies has been presented recently. [5] Light absorption in organic solar cells leads to the generation of excited, bound electron– hole pairs (often called excitons). To achieve substantial energy-conversion efficiencies, these excited electron–hole pairs need to be dissociated into free charge carriers with a high yield. Excitons can be dissociated at interfaces of materials with different electron affinities or by electric fields, or the dissociation can be trap or impurity assisted. Blending conjugated polymers with high-electron-affinity molecules like C60 (as in the bulk-heterojunction solar cell) has proven to be an efficient way for rapid exciton dissociation. Conjugated polymer–C60 interpenetrating networks exhibit ultrafast charge transfer (∼40 fs). [6,7] As there is no competing decay process of the optically excited electron–hole pair located on the polymer in this time regime, an optimized mixture with C60 converts absorbed photons to electrons with an efficiency close to 100%. [8] The associated bicontinuous interpenetrating network enables efficient collection of the separated charges at the electrodes. The bulk-heterojunction solar cell has attracted a lot of attention because of its potential to be a true low-cost photovoltaic technology. A simple coating or printing process would enable roll-to-roll manufacturing of flexible, low-weight PV modules, which should permit cost-efficient production and the development of products for new markets, e.g., in the field of portable electronics. One major obstacle for the commercialization of bulk-heterojunction solar cells is the relatively small device efficiencies that have been demonstrated up to now. [5] The best energy-conversion efficiencies published for small-area devices approach 5%. [9–11] A detailed analysis of state-of-the-art bulk-heterojunction solar cells [8] reveals that the efficiency is limited by the low opencircuit voltage (Voc) delivered by these devices under illumination. Typically, organic semiconductors with a bandgap of about 2 eV are applied as photoactive materials, but the observed open-circuit voltages are only in the range of 0.5–1 V. There has long been a controversy about the origin of the Voc in conjugated polymer–fullerene solar cells. Following the classical thin-film solar-cell concept, the metal–insulator–metal (MIM) model was applied to bulk-heterojunction devices. In the MIM picture, Voc is simply equal to the work-function difference of the two metal electrodes. The model had to be modified after the observation of the strong influence of the reduction potential of the fullerene on the open-circuit volt
4,816 citations
TL;DR: By applying specific fabrication conditions summarized in the Experimental section and post-production annealing at 150°C, polymer solar cells with power-conversion efficiency approaching 5% were demonstrated.
Abstract: By applying the specific fabrication conditions summarized in the Experimental section and post-production annealing at 150 °C, polymer solar cells with power-conversion efficiency approaching 5 % are demonstrated. These devices exhibit remarkable thermal stability. We attribute the improved performance to changes in the bulk heterojunction material induced by thermal annealing. The improved nanoscale morphology, the increased crystallinity of the semiconducting polymer, and the improved contact to the electron-collecting electrode facilitate charge generation, charge transport to, and charge collection at the electrodes, thereby enhancing the device efficiency by lowering the series resistance of the polymer solar cells.
4,513 citations
TL;DR: Because the photoluminescence in the conducting polymer is quenched by interaction with C60, the data imply that charge transfer from the excited state occurs on a picosecond time scale.
Abstract: Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C(60), is reported. After photo-excitation of the conjugated polymer with light of energy greater than the pi-pi* gap, an electron transfer to the C(60) molecule is initiated. Photoinduced optical absorption studies demonstrate a different excitation spectrum for the composite as compared to the separate components, consistent with photo-excited charge transfer. A photoinduced electron spin resonance signal exhibits signatures of both the conducting polymer cation and the C(60) anion. Because the photoluminescence in the conducting polymer is quenched by interaction with C(60), the data imply that charge transfer from the excited state occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures.
4,016 citations