In organic photovoltaics, morphological control of donor and acceptor domains on the nanoscale is key for efficient exciton diffusion and dissociation, carrier transport, and suppression of recombination losses. To realise this, here, we demonstrated a double-fibril network based on ternary donor:acceptor morphology with multi-length scales constructed by combining ancillary conjugated polymer crystallizers and non-fullerene acceptor filament assembly. Using this approach, we achieved an average power conversion efficiency of 19.3% (certified 19.2%). The success lies in the good match between the photoelectric parameters and the morphological characteristic lengths, which utilizes the excitons and free charges efficiently. This strategy leads to enhanced exciton diffusion length (hence exciton dissociation yield) and reduced recombination rate, hence minimizing photon-to-electron losses in the ternary devices as compared to their binary counterparts. The double-fibril network morphology strategy minimizes losses and maximizes the power output, offering the possibility towards 20% power conversion efficiencies in single-junction organic photovoltaics. MainOrganic semiconductors offer the advantage of high optical absorption and tunable energy levels, enabling thin-film solar cells with high light-to-electron conversion efficiencies over a wide range of wavelengths [1][2][3][4] . Desipte recent progresses, the performance of organic solar cells (OSCs) is still limited by non-ideal exciton and charge transport, which depend not only on the electronic structure of organic semiconductors but also on the nanostructure that is formed by material crystallization and phase separation in a bulk heterojunction (BHJ) setting [5][6][7][8] . A suitable sized phase-separated morphology that balances crystalline region and mixing domain on the nanoscale is therefore needed to further push the power conversion efficiency (PCE) of OSCs, however it is a

Single layered organic solar cells (OSCs) using non-fullerene acceptors have This article is protected by copyright. All rights reserved. 35A power conversion efficiency of 16.88% (certified as 16.4%) is achieved based on PM6:Y6 by morphology optimization, which is the top efficient for organic solar cells. Through the study of single structure and film morphology, a well ordered 2D crystal was found, which helps to enhance ultrafast hole and electron transfer, thus improving performance.

Herein, we investigated a series of fullerene-free organic solar cells (OSCs) based on six different donor:acceptor (D:A) blends with varied highest occupied molecular orbital (HOMO) offsets from −0.05 to 0.21 eV. First, to verify the energetic compatibility of a specific D:A pair, especially for HOMO offsets, we established a simple method to estimate the hole transfer tendencies between D and A by using bilayer hole-only devices. It reveals that the asymmetrical diode effect of the bilayer hole-only devices can correlate with the FF and J sc of the relevant OSCs. Second, to find out whether HOMO offset is the main restriction of hole transfer, we measured transient absorption spectra and examined the hole transfer behavior in the blends, revealing that the occurrence of hole transfer is independent of the HOMO offsets and ultrafast in the time scale of ≤4.6 ps for those blends with ≥0 eV HOMO offsets. In contrast, a negative HOMO offset can significantly slow down the hole transfer with a half-time of ∼400 ps. Furthermore, we compare the device parameters under varied light intensities and discover that the bimolecular recombination should be one of the main restrictions for high device performance. Surprisingly, small HOMO offsets of 0 and 0.06 eV can also enable high PCEs of 10.42% and 11.75% for blend 2 (PTQ10:HC-PCIC) and blend 3 (PBDB-TF:HC-PCIC), respectively. Overall, our work demonstrates not only the validity of high-performance OSCs operating at the near zero HOMO offsets but also the charge dynamic insights of these blends, which will help gain understanding on the further improvement of OSCs.

The chemical structure of donors and acceptors limit the power conversion efficiencies achievable with active layers of binary donor-acceptor mixtures. Here, using quaternary blends, double cascading energy level alignment in bulk heterojunction organic photovoltaic active layers are realized, enabling efficient carrier splitting and transport. Numerous avenues to optimize light absorption, carrier transport, and charge-transfer state energy levels are opened by the chemical constitution of the components. Record-breaking PCEs of 18.07% are achieved where, by electronic structure and morphology optimization, simultaneous improvements of the open-circuit voltage, short-circuit current and fill factor occur. The donor and acceptor chemical structures afford control over electronic structure and charge-transfer state energy levels, enabling manipulation of hole-transfer rates, carrier transport, and non-radiative recombination losses.

Manipulating charge generation in a broad spectral region has proved to be crucial for nonfullerene‐electron‐acceptor‐based organic solar cells (OSCs). 16.64% high efficiency binary OSCs are achieved through the use of a novel electron acceptor AQx‐2 with quinoxaline‐containing fused core and PBDB‐TF as donor. The significant increase in photovoltaic performance of AQx‐2 based devices is obtained merely by a subtle tailoring in molecular structure of its analogue AQx‐1. Combining the detailed morphology and transient absorption spectroscopy analyses, a good structure–morphology–property relationship is established. The stronger π–π interaction results in efficient electron hopping and balanced electron and hole mobilities attributed to good charge transport. Moreover, the reduced phase separation morphology of AQx‐2‐based bulk heterojunction blend boosts hole transfer and suppresses geminate recombination. Such success in molecule design and precise morphology optimization may lead to next‐generation high‐performance OSCs.

Low energy loss and efficient charge separation under small driving forces are the prerequisites for realizing high power conversion efficiency (PCE) in organic photovoltaics (OPVs). Here, a new molecular design of nonfullerene acceptors (NFAs) is proposed to address above two issues simultaneously by introducing asymmetric terminals. Two NFAs, BTP‐S1 and BTP‐S2, are constructed by introducing halogenated indandione (A1) and 3‐dicyanomethylene‐1‐indanone (A2) as two different conjugated terminals on the central fused core (D), wherein they share the same backbone as well‐known NFA Y6, but at different terminals. Such asymmetric NFAs with A1‐D‐A2 structure exhibit superior photovoltaic properties when blended with polymer donor PM6. Energy loss analysis reveals that asymmetric molecule BTP‐S2 with six chlorine atoms attached at the terminals enables the corresponding devices to give an outstanding electroluminescence quantum efficiency of 2.3 × 10−2%, one order of magnitude higher than devices based on symmetric Y6 (4.4 × 10−3%), thus significantly lowering the nonradiative loss and energy loss of the corresponding devices. Besides, asymmetric BTP‐S1 and BTP‐S2 with multiple halogen atoms at the terminals exhibit fast hole transfer to the donor PM6. As a result, OPVs based on the PM6:BTP‐S2 blend realize a PCE of 16.37%, higher than that (15.79%) of PM6:Y6‐based OPVs. A further optimization of the ternary blend (PM6:Y6:BTP‐S2) results in a best PCE of 17.43%, which is among the highest efficiencies for single‐junction OPVs. This work provides an effective approach to simultaneously lower the energy loss and promote the charge separation of OPVs by molecular design strategy.

Clean energy production and saving play vital impacts on the sustainability of the global community. Herein, high‐performance semitransparent organic solar cells (ST‐OSCs) with excellent features of power generation, being see‐through, and infrared reflection of heat dissipation, with promising perspectives for building‐integrated photovoltaics (BIPVs) are reported. To simultaneously improve average visible transmittance (AVT) and power conversion efficiency (PCE), formally in a trade‐off relationship, of ST‐OSCs, new ternary blends with alloy‐like near‐infrared (NIR) acceptors are employed, which are effective to improve device efficiency while maintaining visible absorption unchanged, resulting in PCEs of 16.8% for opaque devices and 13.1% for semitransparent OSCs (AVT of 22.4% and infrared photon radiation rejection (IRR) of 77%). Further, multifunctional ST‐OSCs are realized via introducing simple, yet effective photonic reflectors, together with optical simulation, leading to not only perfect fitting of the visible transmittance peak (555 nm) to the photopic response of the human eye but also an excellent IRR of 90% (780–2500 nm), along with 23% AVT and over 12% PCE. This is thought to be the best‐performing multifunctional ST‐OSC with promising prospects as BIPVs in terms of power generation, heat dissipation, and being see‐through.

Semitransparent organic solar cells (ST-OSCs) can potentially meet the huge demands of off-grid and rooftop power supplies for advanced agricultural activities; yet, only a few efforts have been devoted to its development. Herein, we developed a high-performance spectrally engineered ST-OSCs using ''green'' fabrication for greenhouse. Empowered by the newly designed quaternary blends, OSCs were obtained with an excellent power conversion efficiency (PCE) of 17.71%. Such quaternary blends not only exhibit the suitable photon transmission windows for plant absorption but also retain excellent photovoltaic properties upon nonhalogenated solvent fabrication, leading to PCEs of 17.43% for opaque and 13.08% for ST-OSCs (with a plant growth factor of 24.7%), which represent the best-performed OSCs made from non-halogenated solvents. Under the ST-OSCs filtered lights, plants grow favorably, with growth being comparable with that under glass. This work provides an effective approach to constructing organic solar cells with promising features as eco-friendly greenhouse photovoltaics.