The inferior fill factor (FF) is one of main reasons impeding further improvement of power conversion efficiencies (PCEs) in organic solar cells (OSCs). But no theoretical framework for high FFs has been established yet. Herein, an efficient strategy is developed to enhance FFs via introducing a small molecule, CNDT, into active layer to increase electron donor/acceptor interface disorder, raise energy barrier for charge back transfer, and thus reduce bimolecular recombination rate constant (krec). CNDTs tend to distribute over donor/acceptor interfaces and disturb molecular stacking of Y6 to deliver more disordered donor/acceptor interfaces but higher crystal quality in the D18:Y6+ blend film, compared to D18:Y6. Altogether, in the D18:Y6+ blend film, a higher energy of charge transfer state magnifies energy barrier for charge recombination to decrease charge recombination rate/ratio and reduce krec, inhibiting bimolecular recombination in devices. Therefore, FFs of OSCs are improved from 75.78% (D18:Y6) to 81.13% (D18:Y6+), yielding a higher PCE of 19.45%. Moreover, D18:L8-BO+ based OSCs feature FFs over 83%, a record for OSCs so far. PCE increases subsequently to 19.80%. It demonstrates that increasing interface disorder without sacrificing crystal quality enhances energy barrier of charge recombination and inhibits bimolecular recombination to efficiently improve FFs for higher PCEs.

In this work, we propose a novel strategy of introducing luminescent acridine units for central nuclear substitution in quinoxaline-based acceptor molecules (named AQx-o-Ac and AQx-m-Ac) to enhance their photoluminescence quantum yields (PLQY), which can effectively improve the electroluminescent quantum efficiency (EQEEL) of OSCs and thereby suppress Delta Enr. In addition, the substituted acridine unit accelerates molecular aggregation and optimizes molecular crystallization, effectively alleviating the static disorder of acceptor molecules and facilitating charge extraction and transport in OSCs. As a result, the PM6:AQx-m-Ac binary OSCs achieve an excellent PCE of 18.64% with an exceptionally low Delta Enr of 0.166 eV. To the best of our knowledge, a Delta Enr of 0.166 eV represents the lowest value reported for OSCs achieving PCEs over 18 %. Finally, the acceptor AQx-m-Ac is incorporated into PM6:eC9 blend as the third component, and the optimal ternary device produces a superior PCE of 20.28%. This work highlights the potential of promoting luminescence for suppressing nonradiative energy loss and charts a viable path for upcoming breakthrough in high-efficiency organic photovoltaics.

Nonradiative voltage loss (Delta V nr) is a critical factor that limits the efficiency of organic solar cells (OSCs). Introducing highly luminescent materials is a promising approach to reduce Delta V nr. The majority of prior works have focused on enhancing luminescence of low-bandgap nonfullerene acceptors, whereas highly luminescent donors have received far less attention. Herein, we designed and synthesized a highly luminescent polymer donor with aggregation-enhanced emission property, namely PiNTSO-F, and incorporated it into PM6:BTP-eC9-based system. Interestingly, PiNTSO-F was found to locate at the donor-acceptor interface, where it optimizes the interfacial morphology, energetic landscape, and charge dynamics of the active layer. Consequently, the nonradiative recombination rate in the ternary system is significantly reduced, while the interfacial charge generation efficiency is simultaneously improved to nearly unity, effectively minimizing Delta V nr of the device. As a result, the ternary devices achieve a low Delta V nr of 0.192 V and a high efficiency of 20.36%. This work demonstrates an effective strategy for suppressing Delta V nr through developing the highly luminescent polymer donors as a third component, providing mechanistic insights that enable high-performance OSCs with minimized voltage loss.

Cellulose-based materials can be classified as non-conventional luminogens that produce photoluminescence (PL) in the visible range due to specific intermolecular arrangements. Usually such an arrangement is referred to as clusterization. Here, we demonstrate the importance of intramolecular arrangement of ethyl cellulose and bacterial cellulose that demonstrate tunable photoluminescence with multiexponent decay. We show that the observed emission is due to a n-pi* electronic transition of carbonyl groups, whose emission intensity depends on the form of the sample preparation, either the powder-form or spin-coated films, displaying different density of the emitting regions on the microscale. Particularly, it is shown that PL emission is produced from disordered amorphous regions rather than from crystalline ones. We show that the emission is also promoted by mechanical stress applied to the sample that is suggested to facilitate formation of hydrogen-bonded carbonyl groups. The observed stress-assisted emission opens up the potential perspective of using this phenomenon in printed photonic devices.

Herein, a binary cathode interface layer (CIL) strategy based on the industrial solvent fractionated LignoBoost kraft lignin (KL) is adopted for fabrication of organic solar cells (OSCs). The uniformly distributed phenol moieties in KL enable it to easily form hydrogen bonds with commonly used CIL materials, i.e., bathocuproine (BCP) and PFN-Br, resulting in binary CILs with tunable work function (WF). This work shows that the binary CILs work well in OSCs with large KL ratio compatibility, exhibiting equivalent or even higher efficiency to the traditional CILs in state of art OSCs. In addition, the combination of KL and BCP significantly enhanced OSC stability, owing to KL blocking the reaction between BCP and nonfullerene acceptors (NFAs). This work provides a simple and effective way to achieve high-efficient OSCs with better stability and sustainability by using wood-based materials. This work introduces industrial solvent fractionated LignoBoost kraft lignin (KL) in highly efficient organic solar cells (OSCs) by binary cathode interface layer (CIL) strategy, which can significantly improve the stability of both binary and ternary photoactive layer (PAL) OSC, owing to the passivation of diffusion and reaction between bathocuproine (BCP) and nonfullerene acceptors (NFAs). The results combine sustainable wood-based material with classic interface materials in advance NFA-OSCs.image

As a novel class of materials, D-A conjugated macrocycles hold significant promise for chemical science. However, their potential in photovoltaic remains largely untapped due to the complexity of introducing multiple donor and acceptor moieties into the design and synthesis of cyclic pi-conjugated molecules. Here, we report a multiple D-A ring-like conjugated molecule (RCM) via the coupling of dimer molecule DBTP-C3 as a template and thiophenes in high yields. RCM exhibits a narrow optical gap (1.33 eV) and excellent thermal stability, and shows a remarkable photoluminescence yield (phi PL) of 11.1 % in solution, much higher than non-cyclic analogues. Organic solar cell (OSC) constructed with RCM as electron acceptor shows efficient charge separation at donor-acceptor band offsets and achieves a power conversion efficiency (PCE) of 14.2 %-approximately fourfold higher than macrocycle-based OSCs reported so far. This is partly due to low non-radiative voltage loss down to 0.20 eV and a high electroluminescence yield (phi EL) of 4x10-4. Our findings emphasize the potential of D-A cyclic conjugated molecules in advancing organic photovoltaic technology. A multiple D-A ring-like conjugated molecule, RCM was synthesized via a template-directed process. RCM inherits the superior photovoltaic properties characteristic of D-A linear molecules, including a narrow optical gap and effective charge transfer. Importantly, RCM demonstrates reduced non-radiative losses, attributable to its minimized vibration.+image

Non-fullerene acceptors (NFAs) have enabled power conversion efficiencies exceeding 19% in organic solar cells (OSCs). However, the open-circuit voltage of OSCs remains low relative to their optical gap due to excessive non-radiative recombination, and this now limits performance. Here, an important aspect of OSC design is considered, namely management of the triplet exciton population formed after non-geminate charge recombination. By comparing the blends PM6:Y11 and PM6:Y6, it is shown that the greater crystallinity of the NFA domains in PM6:Y11 leads to a higher rate of triplet-triplet annihilation (TTA). This is attributed to the four times larger ground state dipole moment of Y11 versus Y6, which improves the long range NFA out-of-plane ordering. Since TTA converts a fraction of the non-emissive triplet states into bright singlet states, it has the potential to reduce non-radiative voltage losses. Through a kinetic analysis of the recombination processes under 1-Sun illumination, a framework is provided for determining the conditions under which TTA may improve OSC performance. If these could be satisfied, TTA has the potential to reduce non-radiative voltage losses by up to several tens of millivolts.

With the development of photovoltaic materials, especially the small molecule acceptors (SMAs), organic solar cells (OSCs) have made breakthroughs in power conversion efficiencies (PCEs). However, the stability of high-performance OSCs remains a critical challenge for future technological applications. To tackle the inherent instability of SMA materials under the ambient conditions, much effort has been made to improve OSCs stability, including device modification and new materials design. Here we proposed a new electron acceptor design strategy and developed a "quasi-macromolecule" (QM) with an A-pi-A structure, where the functionalized pi-bridge is used as a linker between two SMAs (A), to improve the long-term stability without deteriorating device efficiencies. Such type of QMs enables excellent synthetic flexibility to modulate their optical/electro-chemical properties, crystallization and aggregation behaviors by changing the A and pi units. Moreover, QMs possess a unique long conjugated backbone combining high molecular weight over 3.5 kDa with high purity. Compared with the corresponding SMA BTP-4F-OD (Y6-OD), the devices based on newly synthesized A-pi-A type acceptors QM1 and QM2 could exhibit better device stability and more promising PCEs of 17.05% and 16.36%, respectively. This kind of "molecular-framework" (A-pi-A) structure provides a new design strategy for developing high-efficiency and -stability photovoltaic materials.

Introduction of filler materials into organic solar cells (OSCs) are a promising strategy to improve device performance and thermal/mechanical stability. However, the complex interactions between the state-of-the-art OSC materials and filler require careful selection of filler materials and OSC fabrication to achieve lower cost and improved performance. In this work, the introduction of a natural product betulin-based insulating polymer as filler in various OSCs is investigated. Donor-acceptor-insulator ternary OSCs are developed with improved open-circuit voltage due to decreased trap-assisted recombination. Furthermore, filler-induced vertical phase separation due to mismatched surface energy can strongly affect charge collection at the bottom interface and limit the filler ratio. A quasi-bilayer strategy is used in all-polymer systems to circumvent this problem. Herein, the variety of filler materials in OSCs to biomass is broadened, and the filler strategy is made a feasible and promising strategy toward highly efficient, eco, and low-cost OSCs.

Photovoltaics are one of the most important sustainable energy sources in the 21st century. Among photovoltaics, organic solar cells (OSCs) offer many advantages such as ease of processing, lightweight, the potential for flexibility, and tunable properties. Its peculiar nature and complexity present a fascinating charm, attracting many researchers. Thanks to researchers' efforts, the power conversion efficiency (PCE) of OSCs has been boosted from 1% to 19% during the last three decades. Despite the exciting PCE, some problems remain to be solved, for example, the large voltage loss and long-term stability. The aim of this thesis is to understand the fundamental physics of the state-of-the-art OSCs, especially the loss mechanism. Ultimately, properly understanding the mechanisms will sever as the basis of OSCs further improvements and commercialization. This work focuses on the loss mechanisms of OSCs, particularly the open-circuit voltage and the fill factor. The beginning of this thesis introduces basic concepts regarding semiconductors physics and donor-acceptor OSCs. This part explains how a photon is used to generate electricity and the fundamentals of organic electronics. Subsequently, the detailed balance in a solar cell is reviewed, which is the basis of voltage loss analysis. In this part, we see how the input, recombination, and output form a balance. Then, the way to determine the voltage loss is shown, and the latest understandings in reducing the loss are reviewed. The fill factor, as a measure of the quality of a solar cell, is a complex parameter, especially in OSCs.The latter part of this thesis starts from the photophysical processes in an OSC, and then relates intrinsic parameters to the fill factor. The figure of merits has been employed to express the fill factor analytically. In the end, experimental methods and basic principles for the previous analysis are introduced, including Fourier transform infrared spectroscopy, the external quantum efficiency of photovoltaics (EQEPV), spectrograph for electroluminescence or photoluminescence, transient absorption, and time-delayed collection field. Overall, the thesis combined thermal dynamics and charge dynamics to analyze voltage losses and fill factor losses. The author hopes this work can contribute to a better understanding of the loss mechanisms OSCs.