Innovative molecule design strategy holds promise for the development of next-generation acceptor materials for efficient organic solar cells with low non-radiative energy loss (ΔEnr). In this study, we designed and prepared three novel acceptors, namely BTP-Biso, BTP-Bme and BTP-B, with sterically structured triisopropylbenzene, trimethylbenzene and benzene as side chains inserted into the shoulder of the central core. The progressively enlarged steric hindrance from BTP-B to BTP-Bme and BTP-Biso induces suppressed intramolecular rotation and altered the molecule packing mode in their aggregation states, leading to significant changes in absorption spectra and energy levels. By regulating the intermolecular π-π interactions, BTP-Bme possesses relatively reduced non-radiative recombination rate and extended exciton diffusion lengths. The binary device based on PB2 : BTP-Bme exhibits an impressive power conversion efficiency (PCE) of 18.5 % with a low ΔEnr of 0.19â eV. Furthermore, the ternary device comprising PB2 : PBDB-TF : BTP-Bme achieves an outstanding PCE of 19.3 %. The molecule design strategy in this study proposed new perspectives for developing high-performance acceptors with low ΔEnr in OSCs.
In organic photovoltaic cells, the solution-aggregation effect (SAE) is long considered a critical factor in achieving high power-conversion efficiencies for polymer donor (PD)/non-fullerene acceptor (NFA) blend systems. However, the underlying mechanism has yet to be fully understood. Herein, based on an extensive study of blends consisting of the representative 2D-benzodithiophene-based PDs and acceptor-donor-acceptor-type NFAs, it is demonstrated that SAE shows a strong correlation with the aggregation kinetics during solidification, and the aggregation competition between PD and NFA determines the phase separation of blend film and thus the photovoltaic performance. PDs with strong SAEs enable earlier aggregation evolutions than NFAs, resulting in well-known polymer-templated fibrillar network structures and superior PCEs. With the weakening of PDs' aggregation effects, NFAs, showing stronger tendencies to aggregate, tend to form oversized domains, leading to significantly reduced external quantum efficiencies and fill factors. These trends reveal the importance of matching SAE between PD and NFA. The aggregation abilities of various materials are further evaluated and the aggregation ability/photovoltaic parameter diagrams of 64 PD/NFA combinations are provided. This work proposes a guiding criteria and facile approach to match efficient PD/NFA systems.
Organic photovoltaic (OPV) technology holds tremendous promise as a sustainable power source for underwater off-grid systems. However, research on underwater OPV cells is relatively scarce. Here, this gap is addressed by focusing on the exploration and development of OPV cells specifically designed for underwater applications. An acceptor, named ITO-4Cl, with excellent water resistance, is rationally designed and synthesized. Benefiting from its low energetic disorder and an absorption spectrum well-suited to the underwater environment, the ITO-4Cl-based OPV cell achieves an unprecedented power conversion efficiency (PCE) of over 25.6% at a water depth of 1 m. Additionally, under 660 nm laser irradiation, the cell demonstrates a notable PCE of 31.6%, indicating its potential for underwater wireless energy transfer. Due to the mitigation of thermal effects from solar irradiation, the lifetime of the ITO-4Cl-based OPV cell exceeds 7000 h. Additionally, a flexible OPV cell is fabricated that maintains its initial PCE even under exposure to high pressures of 5 MPa. A 32.5 cm2 flexible module achieves an excellent PCE of 17%. This work fosters a deeper understanding of underwater OPV cells and highlights the promising prospects of OPV cells for underwater applications.
To meet the industrial requirements of organic photovoltaic (OPV) cells, it is imperative to accelerate the development of cost-effective materials. Thiophene-benzene-thiophene central unit-based acceptors possess the advantage of low synthetic cost, while their power conversion efficiency (PCE) is relatively low. Here, by incorporating a para-substituted benzene unit and 1st-position branched alkoxy chains with large steric hindrance, a completely non-fused non-fullerene acceptor, TBT-26, was designed and synthesized. The narrow band gap of 1.38â eV ensures the effective utilization of sunlight. The favorable phase separation morphology of TBT-26-based blend film facilitates the efficient exciton dissociation and charge transport in corresponding OPV cell. Therefore, the TBT-26-based small-area cell achieves an impressive PCE of 17.0 %, which is the highest value of completely non-fused OPV cells. Additionally, we successfully demonstrated the scalability of this design by fabricating a 28.8â cm2 module with a high PCE of 14.3 %. Overall, our work provides a practical molecular design strategy for developing high-performance and low-cost acceptors, paving the way for industrial applications of OPV technology.
Component distribution within the photoactive layer dictates the morphology and electronic structure and substantially influences the performance of organic solar cells (OSCs). In this study, a molecular design strategy is introduced to manipulate component and energetics distribution by adjusting side-chain polarity. Two non-fullerene acceptors (NFAs), ITIC-16F and ITIC-E, are synthesized by introducing different polar functional substituents onto the side chains of ITIC. The alterations result in different distribution tendencies in the bulk heterojunction film: ITIC-16F with intensified hydrophobicity aligns predominantly with the top surface, while ITIC-E with strong hydrophilicity gravitates toward the bottom. This divergence directly impacts the vertical distribution of the excitation energy levels, thereby influencing the excitation kinetics over extended time periods and larger spatial ranges including enhanced diffusion-mediated exciton dissociation and stimulated charge carrier transport. Benefitting from the favorable energy distribution, the device incorporating ITIC-E into the PBQx-TF:eC9-2Cl blend showcases an impressive power conversion efficiency of 19.4%. This work highlights side-chain polarity manipulation as a promising strategy for designing efficient NFA molecules and underscores the pivotal role of spatial energetics distribution in OSC performance.
Organic photovoltaic (OPV) cells have demonstrated remarkable success on the laboratory scale. However, the lack of cathode interlayer materials for large-scale production still limits their practical application. Here, we rationally designed and synthesized a cathode interlayer, named NDI-Ph. Benefiting from their well-modulated work function and self-doping effect, NDI-Ph-based binary OPV cells achieve an excellent power conversion efficiency (PCE) of 19.1%. NDI-Ph can be easily synthesized on a 100 g scale with a low cost of 1.96 $ g-1 using low-cost raw materials and a simple postprocessing method. In addition, the insensitivity to the film thickness of NDI-Ph enables it to maintain a high PCE at various coating speeds and solution concentrations, demonstrating excellent adaptability for high-throughput OPV cell manufacturing. As a result, a module with 21.9 cm2 active area achieves a remarkable PCEactive of 15.8%, underscoring the prospects of NDI-Ph in the large-scale production of OPV cells.
The nonfused thiophene-benzene-thiophene (TBT) unit offers advantages in obtaining low-cost organic photovoltaic (OPV) materials due to its simple structure. However, OPV cells, including TBT-based acceptors, exhibit significantly lower energy conversion efficiencies. Here, we introduce a novel approach involving the design and synthesis of three TBT-based acceptors by substituting different position-branched side chains on the TBT unit. In comparison to TBT-10 and TBT-11, TBT-13, which exclusively incorporates α-position branched side chains with a large steric hindrance, demonstrates a more planar and stable conformation. When blended with the donor PBQx-TF, TBT-13-based blend film achieves favorable π-π stacking and aggregation characteristics, resulting in excellent charge transfer performance in the corresponding device. Due to the simultaneous enhancements in short-circuit current density and fill factor, the TBT-13-based OPV cell obtains an outstanding efficiency of 16.1%, marking the highest value for the cells based on fully nonfused acceptors. Our work provides a practical molecular design strategy for high-performance and low-cost OPV materials.
In the field of organic photovoltaics (OPVs), significant progress has been made in tailoring molecular structures to enhance the open-circuit voltage and the short-circuit current density. However, there remains a crucial gap in the development of coordinated material design strategies focused on improving the fill factor (FF). Here, we introduce a molecular design strategy that incorporates electrostatic potential fluctuation to design organic photovoltaic materials. By reducing the fluctuation amplitude of IT-4F, we synthesized a new acceptor named ITOC6-4F. When using PBQx-TF as a donor, the ITOC6-4F-based cell shows a markedly low recombination rate constant of 0.66×10-14â cm3 s-1 and demonstrates an outstanding FF of 0.816, both of which are new records for binary OPV cells. Also, we find that a small fluctuation amplitude could decrease the energetic disorder of OPV cells, reducing energy loss. Finally, the ITOC6-4F-based cell creates the highest efficiency of 16.0 % among medium-gap OPV cells. Our work holds a vital implication for guiding the design of high-performance OPV materials.
In the realm of organic solar cells (OSCs), the width of the depletion region at the anode interface is a critical factor that adversely impacts the open-circuit voltage (Voc) and the power conversion efficiency (PCE). To address this challenge, a novel approach involving a conjugated polyelectrolyte (CPE)-based composite, PCP-2F-Li:POM, has been developed. This composite serves as a solution-processed hole transport layer (HTL), effectively minimizing the depletion region width in high-performance OSCs. The innovative aspect of PCP-2F-Li:POM lies in its "mutual doping" mechanism. Polyoxometalate (POM) is utilized as a dopant, facilitating the formation of p-doped CPE and n-doped POM within the composite. This results in a substantial increase in doping density, nearly 2 orders of magnitude higher than that observed in unmodified CPE. Consequently, the width of depletion region is markedly reduced, shrinking from 76.4 to 6.0 nm. This reduction plays a pivotal role in enhancing hole transport via the tunneling effect. The practical impact of this development is notable. It leads to an increase in Voc from 0.84 to 0.86 V, thereby contributing significantly to an impressive PCE of 18.04% in OSCs. Moreover, the compatibility of PCP-2F-Li:POM with large-area processing techniques underscores its potential as a viable HTL material for future practical applications. Additionally, its contribution to the enhanced long-term stability of OSCs further bolsters its suitability for practical applications.
Organic solar cells (OSCs) are still suffering from the low light utilization and unstable under ultraviolet irradiation. To tackle these challenges, we design and synthesize a non-fused acceptor based on 1-(2-butyloctyl)-1H-pyrrole as π-bridge unit, denoted as GS70, which serves as active layer in the front-cell for constructing tandem OSCs with a parallel configuration. Benefiting from the well-complementary absorption spectra with the rear-cell, GS70-based parallel tandem OSCs exhibit an improved photoelectron response over the range between 600-700â nm, yielding a high short-circuit current density of 28.4â mA cm-2. The improvement in light utilization translates to a power conversion efficiency of 19.4 %, the highest value among all parallel tandem OSCs. Notably, owing to the intrinsic stability of GS70, the manufactured parallel tandem OSCs retain 84.9 % of their initial PCE after continuous illumination for 1000â hours. Overall, this work offers novel insight into the molecular design of low-cost and stability non-fused acceptors, emphasizing the importance of adopting a parallel tandem configuration for achieving efficient light harvesting and improved photostability in OSCs.
Iodination has unlocked new potentials in organic photovoltaics (OPVs). A newly designed and synthesized iodinated non-fullerene acceptor, BO-4I, showcases exceptional excitation delocalization property with the exciton diffusion length increased to 80â nm. The enhanced electron delocalization property is attributed to the larger atomic radius and electron orbit of the iodine atom, which facilitates the formation of intra-moiety excitations in the acceptor phase. This effectively circumvents the charge transfer state-related recombination mechanisms, leading to a substantial reduction in non-radiative energy loss (ΔEnr ). As a result, OPV cell based on PBDB-TF : BO-4I achieves an impressive efficiency of 18.9 % with a notable ΔEnr of 0.189â eV, markedly surpassing their fluorinated counterparts. This contribution highlights the pivotal role of iodination in reducing energy loss, thereby affirming its potential as a key strategy in the development of advanced next-generation OPV cells.
The ability of achieving high efficiency makes tandem organic photovoltaics (PVs) a competitive technique in potential indoor applications. Except high efficiency, reliable indoor energy supply also calls for outstanding stability. However, unavoidable unstable voltage supply from the circuit control system for indoor light sources like light emitting diodes (LED) and incandescent lamps would cause carrier density fluctuation and device fatigue driven by periodic light/dark switching. In this work, the strobing-induced fatigue within the bulk heterojunction (BHJ)/interconnecting layer (ICL) interface is first revealed and overcome. Based on reliable and effective interfacial doping between conjugated acceptor and metal oxide, the interfacial capacitance that determines the strobing-induced fatigue, has been significantly restrained. The imbalance carrier migration and fierce inter-layer accommodating during the burn-in stage caused by light strobing are substantially diminished. Benefit from this method, the stability of tandem devices is highly enhanced under strobing indoor illumination, and a champion efficiency (35.02%) is obtained. The method provides guidance for further material design for interconnecting layers in organic photovoltaics.
All-polymer solar cells (all-PSCs) possess excellent operation stability and mechanical robustness than other types of organic solar cells, thereby attracting considerable attention for wearable flexible electron devices. However, the power conversion efficiencies (PCEs) of all-PSCs are still lagging behind those of small-molecule-acceptor-based systems owing to the limitation of photoactive materials and unsatisfactory blend morphology. In this work, a novel terpolymer, denoted as PBDB-TFCl (poly4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-bâ³]dithiophene-1,3-bis(2-ethylhexyl)-5,7-di(thiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-câ³]dithiophene-4,8-dione-4,8-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene), is used as an electron donor coupled with a ternary strategy to optimize the performance of all-PSCs. The addition of PBDB-TCl unit deepens the highest occupied molecular orbital energy level, reducing voltage losses. Moreover, the introduction of the guest donor (D18-Cl) effectively regulates the phase-transition kinetics of PBDB-TFCl:D18-Cl:PY-IT during the film formation, leading to ideal size of aggregations and enhanced crystallinity. PBDB-TFCl:D18-Cl:PY-IT devices exhibit a PCE of 18.6% (certified as 18.3%), judged as the highest value so far obtained with all-PSCs. Besides, based on the ternary active layer, the manufactured 36 cm2 flexible modules exhibit a PCE of 15.1%. Meanwhile, the ternary PSCs exhibit superior photostability and mechanical stability. In summary, the proposed strategy, based on molecular design and the ternary strategy, allows optimization of the all-polymer blend morphology and improvement of the photovoltaic performance for stable large-scale flexible PSCs.
To develop the low-cost nonfullerene acceptors (NFAs), two fully non-fused NFAs (TBT-2 and TBT-6) with ortho-bis((2-ethylhexyl)oxy)benzene unit and different side chains onto thiophene-bridges are synthesized through highly efficient synthetic procedures. Both acceptors show good planarity, low optical gaps (≈1.51 eV), and deep highest occupied molecular orbital levels (≤-5.77 eV). More importantly, the single-crystal structure of TBT-2 shows compact molecular arrangement due to the existence of intramolecular interactions between adjacent aromatic units and strong π-π stacking between intermolecular terminal groups. When the two acceptors are fabricated organic photovoltaic (OPV) cells by combining with a wide optical gap polymer donor, the TBT-6 with strong crystallization forms large domain sizes in bulk heterojunction (BHJ) blend. As a result, the TBT-6-based OPV cell shows a low power conversion efficiency (PCE) of 9.53%. In contrast, the TBT-2 with proper crystallization facilitates morphological optimization in the BHJ blend. Consequently, the TBT-2-based OPV cell gives an outstanding PCE of 13.25%, which is one of the best values among OPV cells with similar optical gaps. Overall, this work provides a practical molecular design strategy for developing high-performance and low-cost electron acceptors.
The large depletion region width at the electrode interface may cause serious energy loss in charge collection of organic solar cells (OSCs), depressing the open-circuit voltage and power conversion efficiency (PCE). Herein, a pH neutral solution-processed conjugated polyelectrolyte PIDT-F:IMC as hole transport layer (HTL) to reduce the depletion region width in efficient OSCs is developed. By utilizing "mutual doping" strategy, the doping density of PIDT-F:IMC is increased by more than two orders of magnitude, which significantly reduces the depletion region width at the anode interface from 55 to 7.4 nm, playing an effective role in decreasing the energy loss in hole collection. It is also revealed that the optimal thickness of HTL should be consistent with the depletion region width for achieving the minimum energy loss. The OSC modified by PIDT-F:IMC shows a high PCE of 18.2%, along with an amazing fill factor of 0.79. Moreover, a PCE of 16.5% is achieved in the 1 cm2 OSC by using a blade-coated PIDT-F:IMC HTL, indicating the good compatibility of PIDT-F:IMC with large-area processing technology. The PIDT-F:IMC-modified OCS exhibits a lifetime of 400 h under operational conditions, which is ten times longer than that of the PEDOT:PSS device.
Non-fused electron acceptors have huge advantages in fabricating low-cost organic photovoltaic (OPV) cells. However, morphology control is a challenge as non-fused CâC single bonds bring more molecular conformations. Here, by selecting two typical polymer donors, PBDB-TF and PBQx-TF, the blend morphologies and its impacts on the power conversion efficiencies (PCEs) of non-fused acceptor-based OPV cells are studied. A selenium-containing non-fused acceptor named ASe-5 is designed. The results suggest that PBQx-TF has a lower miscibility with ASe-5 when compared with PBDB-TF. Additionally, the polymer networks may form earlier in the PBQx-TF:ASe-5 blend film due to stronger preaggregation performance, leading to a more obvious phase separation. The PBQx-TF:ASe-5 blend film shows faster charge transfer and suppressed charge recombination. As a result, the PBQx-TF:ASe-5-based device records a good PCE of 14.7% with a higher fill factor (FF) of 0.744, while the PBDB-TF:ASe-5-based device only obtains a moderate PCE of 12.3% with a relatively low FF of 0.662. The work demonstrates that the selection of donors plays a crucial role in controlling the blend morphology and thus improving the PCEs of non-fused acceptor-based OPV cells.
Chlorinated modifications have been extensively employed to modulate the optoelectronic properties of π-conjugated materials. Herein, the Cl substitution in designing nonfullerene acceptors (NFAs) with various bandgaps is studied. Four narrow-bandgap electron acceptors (GS-40, GS-41, GS-42, and GS-43) were synthesized by tuning the electrostatic potential distributions of the molecular conjugated backbones. The optical absorption onset of these NFAs ranges from 900 to 1030 nm. Compared to the nonchlorinated analogue, the introduction of Cl atoms on the core of indaceno[1,2-b:5,6-b'] dithiophene (IDT) and π spacer results in an upward shift of the lowest unoccupied molecular orbital levels and induces a blue shift in the absorption spectra of the NFAs. This alteration facilitates achieving appropriate energy-level alignment and favorable bulk heterojunction morphology when blended with the widely used donor PBDB-TF. The PBDB-TF:GS-43-based solar cells show an optimal power conversion efficiency of 13.3%. This work suggests the potential of employing chlorine-modified IDT and thiophene units as fundamental building blocks for developing high-performance photoactive materials.
Organic photovoltaic (OPV) cells, with highly tunable light-response ranges, offer significant potential for use in driving low-power consumption off-grid electronics in multi-scenarios. However, development of photoactive layer materials that can meet simultaneously the requirements of diverse irradiation conditions is a still challenging task. Herein, a low-cost fully non-fused acceptor (denoted as GS60) featuring well-matched absorption spectra with solar, scattered light and artificial light radiation was designed and synthesized. Systematic characterizations revealed that GS60 possessed outstanding photoelectron properties and ideal morphology, which resulted in reduced voltage loss and suppressed charge recombination. By blending with a non-fused ring polymer PTVT-T, the as-obtained GS60 based OPV cells achieved a good power conversion efficiency (PCE) of 14.1 %, a high value for the cells based on non-fused ring bulk heterojunction. Besides, manufactured large-area OPV modules based on PTVT-T:GS60 yielded PCEs of 11.2 %, 11.8 %, 12.1 %, 23.1 %, and 20.3 % under irradiation of AM 1.5G, natural light of cloudy weather, natural light in shadow, laser and indoor, respectively. The PTVT-T:GS60 devices exhibited considerable potential in terms of improving photostability and reducing material cost. Overall, this work provides novel insight into the molecular design of low-cost non-fused ring acceptors, and extended potential of medium band gap acceptors based OPV cells used in various application scenarios.
Wireless power transfer with collimated power transmission and efficient conversion provides an alternative charging mode for off-grid and portable micro-power electronics. However, charging micro-power electronics with low photon flux can be challenging for current laser power converters. Here we show laser power converters with organic photovoltaic cells with good performance for application in laser wireless power transfer. The laser selection strategy is established and the upper limit of efficiency is proposed. The organic laser power converters exhibit a 36.2% efficiency at a 660 nm laser with a photon flux of 9.5 mW cm-2 and achieve wireless micro power transfer with an output of 0.5 W on a 2 meter scale. This work shows the good performance of organic photovoltaic cells in constructing organic laser power converters and provides a potential solution for the wireless power transfer of micro-power electronics.
Meniscus-guided coating exhibiting outstanding depositing accuracy, functional diversity, and operating convenience is widely used in printing process of photovoltaic electronics. However, current studies about hydrodynamic behaviors of bulk heterojunction ink are still superficial, and the key dynamic parameter dominating film formation is still not found. Here, we establish the principle of accurately evaluate the Hamaker constant and reveal the critical effect of precursor film length in determining flow evolution, the polymer aggregation, and final morphology. A shorter precursor film is beneficial to restraining chain relaxation, enhancing molecular orientation and mobility. On the basis of our precursor film-length prediction method proposed in this work, the optimal coating speed can be accurately traced. Last, a 18.39% power conversion efficiency has been achieved in 3-cm2 cell based on bulk heterojunction fabricated by blade coating, which shows few reduce from 19.40% in a 0.04-cm2 cell based on spin coating.
