The pursuit of low‐cost, flexible, and lightweight renewable power resources has led to outstanding advancements in organic solar cells (OSCs). Among the successful design principles developed for synthesizing efficient conjugated electron donor (ED) or acceptor (EA) units for OSCs, chlorination has recently emerged as a reliable approach, despite being neglected over the years. In fact, several recent studies have indicated that chlorination is more potent for large‐scale production than the highly studied fluorination in several aspects, such as easy and low‐cost synthesis of materials, lowering energy levels, easy tuning of molecular orientation, and morphology, thus realizing impressive power conversion efficiencies in OSCs up to 17%. Herein, an up‐to‐date summary of the current progress in photovoltaic results realized by incorporating a chlorinated ED or EA into OSCs is presented to recognize the benefits and drawbacks of this interesting substituent in photoactive materials. Furthermore, other aspects of chlorinated materials for application in all‐small‐molecule, semitransparent, tandem, ternary, single‐component, and indoor OSCs are also presented. Consequently, a concise outlook is provided for future design and development of chlorinated ED or EA units, which will facilitate utilization of this approach to achieve the goal of low‐cost and large‐area OSCs.
Semi‐transparent organic solar cells (ST‐OSCs) have revolutionized the field of photovoltaics (PVs) due to their unique abilities, such as transparency and color tunability, and have transformed normal power‐harvesting OSC devices into multifunctional devices, such as building‐integrated photovoltaics, agrivoltaics, floating photovoltaics, and wearable electronics. Very recently, ST‐OSCs have seen remarkable progress, with a rapid increase in power conversion efficiency from below 7% to 12–14%, with an average visible transparency of 9–25%, especially due to the use of low bandgap semiconductors including polymer donors and non‐fullerene acceptors that exhibit absorption in the near‐infrared region as photoabsorbent materials. From this perspective, the latest developments in ST‐OSCs stemming from the innovations in photovoltaic materials that delivered multifunctional ST‐OSCs with top‐of‐the‐line power conversion efficiencies are discussed to shed light on the structure‐property relationship between molecular design and current challenges in this cutting‐edge research field. Finally, personal perspectives, including research directions for the future use of ST‐OSCs in multifunctional applications, are also proposed.
Utilizing the N-annulated PDI acceptor PDI–DPP–PDI, a simple air-processed and air-tested organic photovoltaic device fabrication procedure has been established to streamline the screening of donor materials.
A series of small compound materials based on benzodithiophene (BDT) and diketopyrrolopyrrole (DPP) with three different alkyl side chains were synthesized and used for organic photovoltaics. These small compounds had different alkyl branches (i.e., 2-ethylhexyl (EH), 2-butyloctyl (BO), and 2-hexyldecyl (HD)) attached to DPP units. Thin films made of these compounds were characterized and their solar cell parameters were measured in order to systematically analyze influences of the different side chains of compounds on the film microstructure, molecular packing, and hence, charge-transport and recombination properties. The relatively shorter side chains in the small molecules enabled more ordered packing structures with higher crystallinities, which resulted in higher carrier mobilities and less recombination factors; the small molecule with the EH branches exhibited the best semiconducting properties with a power conversion efficiency of up to 5.54% in solar cell devices. Our study suggested that tuning the alkyl chain length of semiconducting molecules is a powerful strategy for achieving high performance of organic photovoltaics.
A set of centrally halogenated oligothiophenes were developed for organic solar cells. The devices with a chlorinated donor (2Cl7T) achieved power conversion efficiencies (PCEs) of up to ca. 11.5% (vs. ca. 2.5% for non-halogenated donor DRCN7T).
A series of four donor-acceptor alternating copolymers based on dialkyloxy-benzothiadiazole (ROBT) as an acceptor and thienoacenes as donor units were synthesized and tested for polymer solar cells (PSCs). These new polymers had different donor units with varied electron-donating ability (thieno[3,2-b]thiophene (TT), dithieno[3,2-b:2',3'-d]thiophene (DTT), benzo[1,2-b:4,5-b']dithiophene (BDT), and naphtha[1,2-b:5,6-b']dithiophene (NDT)) in the polymer backbone. To understand the effect of these thienoacenes on the optoelectronic and photovoltaic properties of the copolymers, we systematically analyzed and compared the energy levels, crystallinity, morphology, charge recombination, and charge carrier mobility in the resulting polymers. In this series, optimized photovoltaic cells yielded power conversion efficiency (PCE) values of 6.25% (TT), 9.02% (DTT), 6.34% (BDT), and 2.29% (NDT) with different thienoacene donors. The introduction of DTT into the thienoacene-ROBT polymer enabled the generation of well-ordered molecular packings with a π-π stacking distance of 3.72 Å, high charge mobilities, and an interconnected nanofibrillar morphology in blend films. As a result, the PSC employing the polymer with DTT exhibited the highest PCE of 9.02%. Thus, our structure-property relationship studies of thienoacene-ROBT-based polymers emphasize that the molecular design of the polymers must be carefully optimized to develop high efficient PSCs. These findings will help us to understand the impact of the donor thienoacene on the optoelectronic and photovoltaic performance of polymers.
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