Bulk Heterojunction Morphology Research Articles

Solid Additive Engineering for Next-generation Organic Photovoltaics.

Solution-processed bulk heterojunction (BHJ) organic solar cells (OSCs) have emerged as a promising next-generation photovoltaic technology. In this emerging field, there is a growing trend of employing solid additives (SAs) to fine-tune the BHJ morphology and unlock the full potential of OSCs. SA engineering offers several significant benefits for commercialization, including the ability to i) control film-forming kinetics to expedite high-throughput fabrication, ii) leverage weak noncovalent interactions between SA and BHJ materials to enhance the efficiency and stability of OSCs, and iii) simplify procedures to facilitate cost-effective production and scaling-up. These features make SA engineering a key catalyst for accelerating the development of OSCs. Recent breakthroughs have shown that SA engineering can achieve an efficiency of 19.67% in single-junction OSCs, demonstrating its effectiveness in promoting the commercialization of organic photovoltaic devices. This review provides a comprehensive overview of significant breakthroughs and pivotal contributions of emerging SAs, focusing on their roles in governing film-forming dynamics, stabilizing phase separation, and addressing other crucial aspects. The rationale and design rules for SAs in highly efficient and stable OSCs are also discussed. Finally, the remaining challenges are summarized, and perspectives on future advances in SA engineering are offered.

Compatibilizer Effects of Strategically Designed Donor–Acceptor Block Copolymers to Enhance the Performance, Stability, and Mechanical Durability of Inverted Organic Solar Cells

AbstractA strategically designed donor–acceptor (D‐A) block copolymer (PM6‐b‐PYIT) is introduced, as a compatibilizer to enhance the performance and stability of inverted organic solar cells (OSCs) consisting of a bulk heterojunction (BHJ) of PM6 and L8‐BO. The PM6‐b‐PYIT compatibilizer not only significantly boosts the power conversion efficiency from 16.32% to 18.02%, but also further modulates the molecular arrangement and improves the compatibility between donor and acceptor materials. This stems from the structural similarity between the copolymer and the host materials, which facilitates ordered molecular stacking and superior charge‐transporting properties, thereby improving the dielectric constant and built‐in voltage and mitigating excessive charge recombination. More importantly, the role of the compatibilizer in stabilizing the BHJ morphology under long‐term aging conditions is highlighted, ascribed to the improved miscibility between different components in the BHJ composite. This in turn renders the photoactive layer more mechanically durable, making it suitable for stretchable applications.

The selenium substitution of solvent additive enables efficient polymer solar cells with efficiency of 19.4 %

Solvent additives, which are widely used as versatile tools for refining active layer morphology, have been considered as important role in enhancing the power conversion efficiency (PCE) of polymer solar cells (PSCs). Herein, innovative solvent additive 2,5-dibromoselenophene (BrS), is devised and synthesized by substituting the sulfur atom in 2,5-dibromothiophene (BrT) with selenium atom. The facile polarization properties of selenium atoms enable selenophene to participate in intermolecular interactions with oxygen or sulfur atoms. Therefore, incorporating BrS into the blend solution leads to refined intermolecular interactions and molecular packing, and crystallinity, resulting in a refined bulk heterojunction (BHJ) morphology compared to using the solvent additives 1-chloronaphthalene (CN) and BrT. Consequently, the BrS outperform their BrT and CN in improving photon absorption, exciton dissociation, and charge collection properties of PSCs, yielding an enhanced PCE of 18.0 % in PM6:Y6 BHJ devices. Moreover, the BrS solvent additive exhibit general applicability in both non-fullerene small molecules PSCs and all-polymer PSCs. High efficiency of 18.8 %, 19.4 % and 18.1 % are obtained in PM6:L8-BO, D18:L8-BO, and PM6:PY-IT BHJ solar cells, respectively, which is rankable among the paramount performance reported to date. Our results highlight the potential of selenophene-based solvent additives as an observable pathway for nanomorphology of active layer and effective enhancement of PCE in PSCs.

Inner/Outer Side Chain Engineering of Non-Fullerene Acceptors for Efficient Large-Area Organic Solar Modules Based on Non-Halogenated Solution Processing in Air.

Achieving efficient and large-area organic solar modules via non-halogenated solution processing is vital for the commercialization yet challenging. The primary hurdle is the conservation of the ideal film-formation kinetics and bulk-heterojunction (BHJ) morphology of large-area organic solar cells (OSCs). A cutting-edge non-fullerene acceptor (NFA), Y6, shows efficient power conversion efficiencies (PCEs) when processed with toxic halogenated solvents, but exhibits poor solubility in non-halogenated solvents, resulting in suboptimal morphology. Therefore, in this study, the impact of modifying the inner and outer side-chains of Y6 on OSC performance is investigated. The study reveals that blending a polymer donor, PM6, with one of the modified NFAs, namely N-HD, achieved an impressive PCE of 18.3% on a small-area OSC. This modified NFA displays improved solubility in o-xylene at room temperature, which facilitated the formation of a favorable BHJ morphology. A large-area (55 cm2) sub-module delivered an impressive PCE of 12.2% based on N-HD using o-xylene under ambient conditions. These findings underscore the significant impact of the modified Y6 derivatives on structural arrangements and film processing over a large-area module at room temperature. Consequently, these results are poised to deepen the comprehension of the scaling challenges encountered in OSCs and may contribute to their commercialization.

20.2% Efficiency Organic Photovoltaics Employing a π-Extension Quinoxaline-Based Acceptor with Ordered Arrangement.

Organic solar cells, as a cutting-edge sustainable renewable energy technology, possess a myriad of potential applications, while the bottleneck problem of less than 20% efficiency limits the further development. Simultaneously achieving an ordered molecular arrangement, appropriate crystalline domain size, and reduced nonradiative recombination poses a significant challenge and is pivotal for overcoming efficiency limitations. This study employs a dual strategy involving the development of a novel acceptor and ternary blending to address this challenge. A novel non-fullerene acceptor, SMA, characterized by a highly ordered arrangement and high lowest unoccupied molecular orbital energy level, is synthesized. By incorporating SMA as a guest acceptor in the PM6:BTP-eC9 system, it is observed that SMA staggered the liquid-solid transition of donor and acceptor, facilitating acceptor crystallization and ordering while maintaining a suitable domain size. Furthermore, SMA optimized the vertical morphology and reduced bimolecular recombination. As a result, the ternary device achieved a champion efficiency of 20.22%, accompanied by increased voltage, short-circuit current density, and fill factor. Notably, a stabilized efficiency of 18.42% is attained for flexible devices. This study underscores the significant potential of a synergistic approach integrating acceptor material innovation and ternary blending techniques for optimizing bulk heterojunction morphology and photovoltaic performance.

Polymer Fiber Rigid Network with High Glass Transition Temperature Reinforces Stability of Organic Photovoltaics

HighlightsA unique approach is proposed: constructing a polymer fiber rigid network with high glass transition temperature.Frozen bulk heterojunction morphology impeded deterioration of exciton quenching, charge transport, and charge extraction properties during thermal aging. The strategy is universal and can be further optimized for enhanced thermal stability and improved mechanical resilience.

Ternary Polymer Solar Cells: Impact of Non-Fullerene Acceptors on Optical and Morphological Properties

Ternary organic solar cells contain a single three-component photoactive layer with a wide absorption window, achieved without the need for multiple stacking. However, adding a third component into a well-known binary blend can influence the energetics, optical window, charge carrier transport, crystalline order and conversion efficiency. In the form of binary blends, the low-bandgap regioregular polymer donor poly(3-hexylthiophene-2,5-diyl), known as P3HT, is combined with the acceptor PC61BM, an inexpensive fullerene derivative. Two different non-fullerene acceptors (ITIC and eh-IDTBR) are added to this binary blend to form ternary blends. A systematic comparison between binary and ternary systems was carried out as a function of the thermal annealing temperature of organic layers (100 °C and 140 °C). The power conversion efficiency (PCE) is improved due to increased fill factor (FF) and open-circuit voltage (Voc) for thermal-annealed ternary blends at 140 °C. The transport properties of electrons and holes were investigated in binary and ternary blends following a Space-Charge-Limited Current (SCLC) protocol. A favorable balanced hole–electron mobility is obtained through the incorporation of either ITIC or eh-IDTBR. The charge transport behavior is correlated with the bulk heterojunction (BHJ) morphology deduced from atomic force microscopy (AFM), contact water angle (CWA) measurement and 2D grazing-incidence X-ray diffractometry (2D-GIXRD).

Optical and photovoltaic properties of organic solar cells versus bulk-heterojunction morphology

Optical and photovoltaic properties of organic solar cells versus bulk-heterojunction morphology

Over 19 % Efficiency Organic Solar Cells Enabled by Manipulating the Intermolecular Interactions through Side Chain Fluorine Functionalization.

Fluorine side chain functionalization of non-fullerene acceptors (NFAs) represents an effective strategy for enhancing the performance of organic solar cells (OSCs). However, a knowledge gap persists regarding the relationship between structural changes induced by fluorine functionalization and the resultant impact on device performance. In this work, varying amounts of fluorine atoms were introduced into the outer side chains of Y-series NFAs to construct two acceptors named BTP-F0 and BTP-F5. Theoretical and experimental investigations reveal that side-chain fluorination significantly increase the overall average electrostatic potential (ESP) and charge balance factor, thereby effectively improving the ESP-induced intermolecular electrostatic interaction, and thus precisely tuning the molecular packing and bulk-heterojunction morphology. Therefore, the BTP-F5-based OSC exhibited enhanced crystallinity, domain purity, reduced domain spacing, and optimized phase distribution in the vertical direction. This facilitates exciton diffusion, suppresses charge recombination, and improves charge extraction. Consequently, the promising power conversion efficiency (PCE) of 17.3 % and 19.2 % were achieved in BTP-F5-based binary and ternary devices, respectively, surpassing the PCE of 16.1 % for BTP-F0-based OSCs. This work establishes a structure-performance relationship and demonstrates that fluorine functionalization of the outer side chains of Y-series NFAs is a compelling strategy for achieving ideal phase separation for highly efficient OSCs.

Sequential Deposition Processing to Control Vertical Composition Distribution toward High‐Performance and Stable Inverted Organic Solar Cells

AbstractSequential deposition (SD) is widely applied in the fabrication of high‐performance organic solar cells (OSCs). Nevertheless, the feasibility of SD in inverted photovoltaic devices is rarely mentioned. Moreover, the vertical component distribution in SD‐processed devices is still under debate. This study demonstrates that SD can achieve the entire bulk heterojunction morphology by precisely controlling the morphology of the active layer. To further promote photovoltaic performance, two post treatments, thermal annealing (TA) and solvent vapor annealing (SVA), are conducted to compare their effects on SD‐processed inverted photovoltaic devices. The results verify that SD can significantly enhance the thermal stability of devices. This work provides a valuable insight for systematically understanding SD processing and the preparation of stable inverted OSCs with superior performance.

Non-halogenated and non-volatile solid additive for improving the efficiency and stability of organic solar cells

A non-halogenated and non-volatile solid additive PID can interact simultaneously with donor and acceptor molecules and stabilize the bulk-heterojunction morphology, increasing the efficiency and thermal stability of organic solar cell devices.

Design of Chlorinated Indaceno[1,2-b:5,6-b']dithiophene Acceptors toward Efficient Organic Photovoltaics.

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.

Selectively Modulating Componential Morphologies of Bulk Heterojunction Organic Solar Cells.

Achieving precise control over the nanoscale morphology of bulk heterojunction films presents a significant challenge for the conventional post-treatments employed in organic solar cells (OSCs). In this study, a near-infrared photon-assisted annealing (NPA) strategy is developed for fabricating high-performance OSCs under mild processing conditions. It is revealed a top NIR light illumination, together with the bottom heating, enables the selective tuning of the molecular arrangement and assembly of narrow bandgap acceptors in polymer networks to achieve optimal morphologies, as well as the acceptor-rich top surface of active layers. The derived OSCs exhibit a remarkable power conversion efficiency (PCE) of 19.25%, representing one of the highest PCEs for the reported binary OSCs so far. Moreover, via the NPA strategy, it has succeeded in accessing top-illuminated flexible OSCs using thermolabile polyethylene terephthalate from mineral water bottles, displaying excellent mechanical stabilities. Overall, this work will hold the potential to develop organic solar cells under mild processing with various substrates.

PC71BM as Morphology Regulator for Highly Efficient Ternary Organic Solar Cells with Bulk Heterojunction or Layer-by-Layer Configuration.

The ternary strategy is one of the effective methods to regulate the morphology of the active layer in organic solar cells (OSCs). In this work, the ternary OSCs with bulk heterojunction (BHJ) or layer-by-layer (LbL) active layers are prepared by using the polymer donor PM6 and the non-fullerene acceptor L8-BO as the main system and the fullerene acceptor PC71BM as the third component. The power conversion efficiencies (PCEs) of BHJ OSCs and LbL OSCs are increased from 17.10% to 18.02% and from 17.20% to 18.20% by introducing PC71BM into the binary active layer, respectively. The in situ UV-vis absorption spectra indicate that the molecular aggregation and crystallization process can be prolonged by introducing PC71BM into the PM6:L8-BO or PM6/L8-BO active layer. The molecular orientation and molecular crystallinity in the active layer are optimized by introducing the PC71BM into the binary BHJ or LbL active layers, which can be confirmed by the experimental results of grazing incidence wide-angle X-ray scattering. This study demonstrates that the third component PC71BM can be used as a morphology regulator to regulate the morphology of BHJ or LbL active layers, thus effectively improving the performance of BHJ and LbL OSCs.

Influences of Metal Electrodes on Stability of Non‐Fullerene Acceptor‐Based Organic Photovoltaics

AbstractUnderstanding chemical degradation at the interface between different layers in an organic photovoltaic device (OPV) is crucial to improving the long‐term stability of OPVs. Herein, molecular‐level insights are provided into the impact of different metal top electrodes on the interfacial morphology and stability of photoactive layers in PM6:Y6 bulk‐heterojunction (BHJ) OPVs. OPVs with an aluminum (Al) top electrode exhibit inferior stability compared to silver (Ag) electrode devices upon thermal annealing, whereby thermal stress induces the diffusion of both Al and Ag atoms to the PM6:Y6 BHJ layer. The diffused Al atoms cause surface recombination at the interface between the photoactive layer and an interlayer. Specifically, X‐ray photoelectron spectroscopy suggests the different local chemical environments of PM6 and Y6 moieties in PM6:Y6/Al‐contact devices. These results are corroborated by solid‐state nuclear magnetic resonance and electron paramagnetic resonance spectroscopy measurements, indicating the formation of ionic and organo‐metallic‐like species at the sub‐layers of the PM6:Y6 BHJ morphology, which are estimated to be less than 5 wt% of the PM6:Y6/Al blend. By comparison, the Ag atoms do not adversely affect PM6:Y6 BHJ morphology and the associated device physics. The investigation of reactive electrode‐BHJ interfaces by multiscale characterization techniques and device physics is expected to provide guidance to future interfacial engineering strategies to develop stable and efficient OPVs.

Enhanced performance of organic solar cells through incorporation of MoS2 nanoparticles in bulk heterojunction layer

In this work, MoS2 nanoparticles were incorporated in P3HT:PC61BM bulk heterojunction (BHJ) layers and the effect of their concertation on BHJ morphology and structure, its optical absorption spectra and photovoltaic characteristics of P3HT:PC61BM BHJ solar cells were investigated in detail. MoS2 nanoparticles were deposited by laser ablation of MoS2 powders in chlorobenzene. AFM and optical absorption study indicates that an addition of MoS2 nanoparticles in BHJ results in an improved crystallinity and a decreased defect density. The volt-ampere measurements of BHJ solar cells shows that the increase in the MoS2 concertation up to 0.5 wt% leads to the boost of photovoltaic characteristics and a champion device, based on BHJ with MoS2 nanoparticles at concertation 0.5 wt %, generated the power conversion efficiency about 3%, which 3 times higher than an efficiency of a device based on pristine BHJ. The impedance spectroscopy (IS) technique was used to understand the effect of MoS2 nanoparticles on the charge transport mechanism. IS study revealed that a resistance of the BHJ layer slightly and steadily grows by increasing the concentration of MoS2 nanoparticles, whereas a recombination resistance determining the charge recombination rate increases reaching maximum value at the MoS2 concertation of 0.5 wt %. A further growth in the MoS2 concertation results in a decrease of the recombination resistance indicating an acceleration of charge recombination rate. The influence of conductivity nature of MoS2 nanoparticles and their distribution in the BHJ layer on charge transport mechanism is also discussed.

Efficient Integrated Perovskite/Organic Solar Cells via Interdigitated Interfacial Charge Transfer.

The architecture of integrated perovskite/organic solar cells (IPOSCs) is a promising strategy to further enhance the power conversion efficiency (PCE) by extending their photoresponse to the near-infrared range. To maximize the potential benefits of the system, it is crucial to optimize the perovskite crystallinity and intimate morphology of the organic bulk heterojunction (BHJ). More importantly, efficient charge transfer between the interface of the perovskite and BHJ plays a key role in the success of IPOSCs. This paper reports efficient IPOSCs by forming interdigitated interfaces between the perovskite and BHJ layers. Large microscale perovskite grains enable the infiltration of BHJ materials into the perovskite grain boundary, thereby increasing the interface area and promoting efficient charge transfer. Owing to the synergetic effect of the interdigitated interfaces and optimized BHJ nanomorphology, the developed P-I-N-type IPOSC exhibited an excellent PCE of 18.43% with a Jsc of 24.44 mA/cm2, a Voc of 0.95 V, and a FF of 79.49%, which is one of very efficient hybrid perovskite-polymer solar cells.

Morphology manipulation of photoactive layer through block copolymer to improve the photovoltaic performances of polymer solar cells

Additive treatment is an effective method for manipulating the bulk heterojunction (BHJ) photoactive layer morphology of polymer solar cells (PSCs). In this work, block copolymer, polystyrene-block-poly(acrylic acid) (PS-b-PAA), was elaborately selected (according to Flory–Huggins theory) as an additive for active layer to manipulate the BHJ morphology and to enhance the photovoltaic performance of devices. As results, with a PS-b-PAA concentration of 0.4 mg/ml, the corresponding devices achieve a significant power conversion efficiency (PCE) improvement to 13.08%. By systematically analysis, the improved PCE can be ascribed to more appreciate phase separation induced by incorporation of PS-b-PAA. For the instance of the photovoltaic physical process, more suitable morphology can induce improved charge transport efficiency, suppressed bimolecular recombination and monomolecular recombination or trap-assisted recombination. In comparing, the photovoltaic performance of devices with PS-b-PAA is obviously better than that of devices with insulating polymer polystyrene (PS) and polyacrylic acid (PAA). Hence, this work checks the morphology manipulation effects of block copolymer PS-b-PAA and provides an effective and facile method to improve the morphology and photovoltaic performances of PSCs.

Trifluoromethyl-Substituted Conjugated Random Terpolymers Enable High-Performance Small and Large-Area Organic Solar Cells Using Halogen-Free Solvent.

The advancement of non-fullerene acceptors with crescent-shaped geometry has led to the need for polymer donor improvements. Additionally, there is potential to enhance the photovoltaic parameters in high-efficiency organic solar cells (OSCs). The random copolymerization method is a straightforward and effective strategy to further optimize photoactive morphology and enhance device performance. However, finding a suitable third component in terpolymers remains a crucial challenge. In this study, a series of terpolymer donors (PTF3, PTF5, PTF10, PTF20, and PTF50) is synthesized by introducing varying amounts of the trifluoromethyl-substituted unit (CF3) into the PM6 polymer backbone. Even subtle changes in the CF3 content can significantly enhance all the photovoltaic parameters due to the optimized energy levels, molecular aggregation/miscibility, and bulk-heterojunction morphology of the photoactive materials. Thus, the best binary OSC based on the PTF5:Y6-BO achieves an outstanding power conversion efficiency (PCE) of 18.2% in the unit cell and a PCE of 11.6% in the sub-module device (aperture size: 54.45 cm2 ), when using halogen-free solvent o-xylene. This work showcases the remarkable potential of the easily accessible CF3 unit as a key constituent in the construction of terpolymer donors in high-performance OSCs.

Asymmetric Polymer Additive for Morphological Regulation and Thermally Stable Organic Solar Cells.

High thermal stability is crucial for the commercialization of organic solar cells (OSCs). The thermal stability of OSCs has been improved using the tailoring blend morphology of bulk heterojunctions (BHJs). Herein, we demonstrated thermally stable OSCs in a ternary blended system containing low-crystalline semiconducting polymers (asy-PNDI1FTVT and PTB7-Th) and a non-fullerene acceptor (Y6). The asymmetric n-type semiconducting polymer (asy-PNDI1FTVT) differed from general symmetric semiconducting polymers as it randomly substituted fluorine atoms at the donor moiety (TVT), resulting in significantly lower crystallinity. asy-PNDI1FTVT in PTB7-Th:Y6 exhibited a well-mixed morphology at the BHJ and efficiently facilitated the charge dissociation process with an enhanced fill factor and power conversion efficiency. Furthermore, the ternary system of PTB7-Th:Y6:asy-PNDI1FTVT suppressed phase separation with negligible burn-in loss and performance degradation under thermal stress. The experiments showed that our devices without encapsulation retained over 90% of their initial efficiencies after 100 h at 65 °C. These results show significant potential for the development of thermally stable OSCs with reasonable efficiency.