Impact of Electrostatic Interaction on Bulk Morphology in Efficient Donor-Acceptor Photovoltaic Blends.

Bulk heterojunctions comprising mixed donor (D) and acceptor (A) materials have proven to be the most efficient device structures for organic photovoltaic (OPV) cells. The bulk morphology of such cells plays a key role in charge generation, recombination, and transport, thus determining the device performance. Although numerous studies have discussed the morphology-performance relationship of these cells, the method of designing OPV materials with the desired morphology remains unclear. Herein, guided by molecular electrostatic potential distributions, we have established a connection between the chemical structure and bulk morphology. We show that the molecular orientation at the D-A interface and the domain purity in the blend can be effectively modulated by modifying the functional groups. Enhancing the D-A interaction is beneficial for charge generation. However, the resulting low domain purity and increased charge transfer ratio in its hybridization with the local excitation states lead to severe charge recombination. Fine-tuning the bulk morphology can give balanced charge generation and recombination, which is crucial for further boosting the efficiency of the OPV cells.

Tuning the Hybridization of Local Exciton and Charge-Transfer States in Highly Efficient Organic Photovoltaic Cells.

Decreasing the energy loss is one of the most feasible ways to improve the efficiencies of organic photovoltaic (OPV) cells. Recent studies have suggested that non-radiative energy loss ( E non - rad loss ) is the dominant factor that hinders further improvements in state-of-the-art OPV cells. However, there is no rational molecular design strategy for OPV materials with suppressed E non - rad loss . Herein, taking molecular surface electrostatic potential (ESP) as a quantitative parameter, we establish a general relationship between chemical structure and intermolecular interactions. The results reveal that increasing the ESP difference between donor and acceptor will enhance the intermolecular interaction. In the OPV cells, the enhanced intermolecular interaction will increase the charge-transfer (CT) state ratio in its hybridization with the local exciton state to facilitate charge generation, but simultaneously result in a larger E non - rad loss . These results suggest that finely tuning the ESP of OPV materials is a feasible method to further improve the efficiencies of OPV cells.

14.7% Efficiency Organic Photovoltaic Cells Enabled by Active Materials with a Large Electrostatic Potential Difference.

Although significant improvements have been achieved for organic photovoltaic cells (OPVs), the top-performing devices still show power conversion efficiencies far behind those of commercialized solar cells. One of the main reasons is the large driving force required for separating electron-hole pairs. Here, we demonstrate an efficiency of 14.7% in the single-junction OPV by using a new polymer donor PTO2 and a nonfullerene acceptor IT-4F. The device possesses an efficient charge generation at a low driving force. Ultrafast transient absorption measurements probe the formation of loosely bound charge pairs with extended lifetime that impedes the recombination of charge carriers in the blend. The theoretical studies reveal that the molecular electrostatic potential (ESP) between PTO2 and IT-4F is large, and the induced intermolecular electric field may assist the charge generation. The results suggest OPVs have the potential for further improvement by judicious modulation of ESP.

A New Polymer Donor Enables Binary All-Polymer Organic Photovoltaic Cells with 18% Efficiency and Excellent Mechanical Robustness.

The development of polymerized small-molecule acceptors has boosted the power conversion efficiencies (PCEs) of all-polymer organic photovoltaic (OPV) cells to 17%. However, the polymer donors suitable for all-polymer OPV cells are still lacking, restricting the further improvement of their PCEs. Herein, a new polymer donor named PQM-Cl is designed and its photovoltaic performance is explored. The negative electrostatic potential and low average local ionization energy distribution of the PQM-Cl surface enable efficient charge generation and transfer process. When blending with a well-used polymer acceptor, PY-IT, the PQM-Cl-based devices deliver an impressive PCE of 18.0% with a superior fill factor of 80.7%, both of which are the highest values for all-polymer OPV cells. The relevant measurements demonstrate that PQM-Cl-based films possess excellent mechanical and flexible properties. As such, PQM-Cl-based flexible photovoltaic cells are fabricated and an excellent PCE of 16.5% with high mechanical stability is displayed. These results demonstrate that PQM-Cl is a potential candidate for all-polymer OPV cells and provide insights into the design of polymer donors for high-efficient all-polymer OPV cells.

A Tandem Organic Photovoltaic Cell with 19.6% Efficiency Enabled by Light Distribution Control.

Despite more potential in realizing higher photovoltaic performance, the highest power conversion efficiency (PCE) of tandem organic photovoltaic (OPV) cells still lags behind that of state-of-the-art single-junction cells. In this work, highly efficient double-junction tandem OPV cells are fabricated by optimizing the photoactive layers with low voltage losses and developing an effective method to tune optical field distribution. The tandem OPV cells studied are structured as indium tin oxide (ITO)/ZnO/bottom photoactive layer/interconnecting layer (ICL)/top photoactive layer/MoOx /Ag, where the bottom and top photoactive layers are based on blends of PBDB-TF:ITCC and PBDB-TF:BTP-eC11, respectively, and ICL refers to interconnecting layer structured as MoOx /Ag/ZnO:PFN-Br. As these results indicate that there is not much room for optimizing the bottom photoactive layer, more effort is put into fine-tuning the top photoactive layer. By rationally modulating the composition and thickness of PBDB-TF:BTP-eC11 blend films, the 300 nm-thick PBDB-TF:BTP-eC11 film with 1:2 D/A ratio is found to be an ideal photoactive layer for the top sub-cell in terms of photovoltaic characteristics and light distribution control. For the optimized tandem cell, a PCE of 19.64% is realized, which is the highest result in the OPV field and certified as 19.50% by the National Institute of Metrology.

18.5% Efficiency Organic Solar Cells with a Hybrid Planar/Bulk Heterojunction.

The donor:acceptor heterojunction has proved as the most successful approach to split strongly bound excitons in organic solar cells (OSCs). Establishing an ideal architecture with selective carrier transport and suppressed recombination is of great importance to improve the photovoltaic efficiency while remains a challenge. Herein, via tailoring a hybrid planar/bulk structure, highly efficient OSCs with reduced energy losses (Eloss s) are fabricated. A p-type benzodithiophene-thiophene alternating polymer and an n-type naphthalene imide are inserted on both sides of a mixed donor:acceptor active layer to construct the hybrid heterojunction, respectively. The tailored structure with the donor near the anode and the acceptor near the cathode is beneficial for obtaining enhanced charge transport, extraction, and suppressed charge recombination. As a result, the photovoltaic characterizations suggest a reduced nonradiative Eloss by 25 meV, and the best OSC records a high efficiency of 18.5% (certified as 18.2%). This study highlights that precisely regulating the structure of donor:acceptor heterojunction has the potential to further improve the efficiencies of OSCs.

Single-Junction Organic Photovoltaic Cell with 19% Efficiency.

Improving power conversion efficiency (PCE) is important for broadening the applications of organic photovoltaic (OPV) cells. Here, a maximum PCE of 19.0% (certified value of 18.7%) is achieved in single-junction OPV cells by combining material design with a ternary blending strategy. An active layer comprising a new wide-bandgap polymer donor named PBQx-TF and a new low-bandgap non-fullerene acceptor (NFA) named eC9-2Cl is rationally designed. With optimized light utilization, the resulting binary cell exhibits a good PCE of 17.7%. An NFA F-BTA3 is then added to the active layer as a third component to simultaneously improve the photovoltaic parameters. The improved light unitization, cascaded energy level alignment, and enhanced intermolecular packing result in open-circuit voltage of 0.879 V, short-circuit current density of 26.7 mA cm-2 , and fill factor of 0.809. This study demonstrates that further improvement of PCEs of high-performance OPV cells requires fine tuning of the electronic structures and morphologies of the active layers.

Carbonyl Bridge-Based p-π Conjugated Polymers as High-Performance Electrodes of Organic Lithium-Ion Batteries.

Organic redox compounds have shown promising potential as electrode materials for lithium-ion batteries. Polymerization is an effective and feasible method to prevent rapid capacity decay. However, present conjugated polymers and nonconjugated polymers have their own limitations to constructing stable and high-performance electrodes. Herein, we report a novel polyimide NDI-O, which is connected by carbonyl bridges. The NDI-O is a p-π conjugated polymer that exhibits a high gravimetric energy density of 542 W h kg-1 and an ultrahigh power density of 14,000 W kg-1 due to its intriguing electronic properties. The combination of molecular electrostatic potential calculations and ex situ technologies reveals the lithium-ion storage mechanism during the charge and discharge processes. The orbital distribution calculations and electrochemical impedance spectroscopy tests have been shown to verify the excellent kinetic properties of NDI-O. This work expands the scope of polymers applied for LIBs and provides new methods to construct high-performance electrode materials for sustainable batteries.

High-Efficiency Nonfullerene Organic Solar Cells Enabled by 1000 nm Thick Active Layers with a Low Trap-State Density.

The high-efficiency organic solar cells (OSCs) with thicker active layers are potential candidates for the fabrication of large-area solar panels. The low charge carrier mobility of the photoactive materials has been identified as the major problem hindering the photovoltaic performance of the thick-film OSCs. In this study, high performance of ultra-thick-film OSCs employing a nonfullerene acceptor BTP-4Cl and a polymer donor PBDB-TF is demonstrated. Two blends (PBDB-TF:BTP-4Cl and PBDB-TF:IT-4F) show comparable mobilities and excellent photovoltaic characteristics in thin-film devices, while in the 1000 nm thick devices, although they both exhibit desirable and balanced mobilities, the PBDB-TF:BTP-4Cl-based blend possesses lower trap-state density than the IT-4F-based counterpart, leading to lower trap-assist recombination, longer carrier lifetime, and thus a much higher short-circuit current density in the device. As a result, the BTP-4Cl-based 1000 nm thick OSC achieves a remarkable power conversion efficiency of 12.1%, which greatly outperforms the IT-4F-based devices (4.72%). Furthermore, for a 1000 nm thick device with an active area of 4 cm2, a promising efficiency of 10.1% was obtained, showing its great potential in future large-scale production.

p-Doped Conducting Polyelectrolyte as an Anode Interlayer Enables High Efficiency for 1 cm2 Printed Organic Solar Cells.

Manufacturing large-area devices through a low-cost and large batch printing technique is the key to the commercialization of organic solar cells (OSCs). However, the lack of printable anode interlayer (AIL) materials severely impedes the development of high-efficiency printed OSCs. Herein, we synthesize three p-type self-doped conjugated polyelectrolytes (CPEs), namely, PCP-B, PCP-2B, and PCP-3B, as printable AIL materials for fabricating high-performance and large-area OSCs. By increasing the number of benzene units in the polymer backbone, the work function of the CPEs was enhanced from 4.57 to 5.01 eV, and the optical transparency was also improved because of the enlarged polymer band gap. The improved photoelectronic properties as well as a good film-forming capacity make the PCP-3B an ideal AIL material to be processed by the printing technique. By using PCP-3B, a 1 cm2 printed device was fabricated in which all the functional layers, including the AIL, active layer, and cathode interlayer were processed by blade-coating, achieving a power conversion efficiency (PCE) of 9.67%. The PCE belongs to the highest efficiency at present for printable large-area OSCs, showing a promising prospect for the OSC mass production.

Enhanced π-π Interactions of Nonfullerene Acceptors by Volatilizable Solid Additives in Efficient Polymer Solar Cells.

Fine-tuning of the nanoscale morphologies of the active layers in polymer solar cells (PSCs) through various techniques plays a vital role in improving the photovoltaic performance. However, for emerging nonfullerene (NF) PSCs, the morphology optimization of the active-layer films empirically follows the methods originally developed in fullerene-based blends and lacks systematic studies. In this work, two solid additives with different volatilities, SA-4 and SA-7, are applied to investigate their influence on the morphologies and photovoltaic performances of NF-PSCs. Although both solid additives effectively promote the molecular packing of the NF acceptors, due to the higher volatility of SA-4, the devices processed with SA-4 exhibit a power conversion efficiency of 13.5%, higher than that of the control devices, and the devices processed with SA-7 exhibit poor performances. Through a series of detailed morphological analyses, it is found that the volatilization of SA-4 after thermal annealing is beneficial for the self-assembly packing of acceptors, while the residuals due to the incomplete volatilization of SA-7 have a negative effect on the film morphology. The results delineate the feasibility of applying volatilizable solid additives and provide deeper insights into the working mechanism, establishing guidelines for further material design of solid additives.