Morphology Of Blend Films Research Articles

High‐Performance Organic Solar Cells Enabled by 3D Globally Aromatic Carboranyl Solid Additive

AbstractA key factor in optimizing organic solar cells (OSCs) is the precise control of blend film morphology to enhance exciton dissociation and charge transport. Solid additives play a vital role in this process, with 3D polyhedral or spherical molecules being ideal candidates due to their delocalized π‐orbitals and omnidirectional charge transport. However, the application of classical fullerene derivatives as spherical additives is limited by their synthetic complicacy and poor solubility. Herein, the potential of 3D globally aromatic carboranyl cages as solid additives, specifically 1‐amino‐o‐carborane (CB‐NH2) and 1‐carboxy‐o‐carborane (CB‐COOH), is explored to fine‐tune the film morphology and improve the performance of OSCs. These spherical molecules provide an extensive surface for hydrogen bonding interactions, which serve as the driving force for manipulating the vertical phase separation and active layer crystallinity. Remarkably, CB‐NH2‐processed devices with well‐tuned morphology yield a remarkable power conversion efficiency of 19.48%, highlighting the effectiveness of 3D carboranyl additives on improving OSC performance. This work challenges the reliance on fullerene derivatives as spherical additives and offers new insights into the mechanisms by which 3D globally aromatic additives can achieve high performance in OSCs, emphasizing the significance of molecular engineering in the development of next‐generation solar cell technology.

Enhancing the photovoltaic performance of dithienobenzodithiophene based polymer donors through backbone fluorination and radical polymer additives

Unveiling the corresponding relationship between the molecular architecture of organic semiconductor materials and the morphology within the active layer of the organic solar cells (OSCs) is essential for the innovation of novel optical materials and the refinement of device optimization strategies to overcome the bottlenecks in efficiency. In this work, three dithieno[3,2-b]benzo[1,2-b;4,5-b’]dithiophene(DTBDT)-alt-benzothiadiazole (BT) based polymer donors (PDTBDT-F-BT, PDTBDT-F-FBT, and PDTBDT-F-2FBT) with varying fluorine atom content within their acceptor segments were designed and synthesized, and the photovoltaic performances of these polymers when blended with Y6 were meticulously investigated. Incorporating fluorine atoms into the BT segment was observed to not only incrementally increase the optical bandgap, lower the HOMO energy level, and bolster the self-aggregation of the polymer, but also effectively reduce the surface energy of the resulting polymer, thereby altering the donor-acceptor (D-A) interfacial spacing and the phase separation in the blend films as illustrated by molecular dynamic simulations and morphology characterization. As a result, the OSCs fabricated using PDTBDT-F-FBT, which incorporates a single fluorine substitution in the BT unit, demonstrated the highest power conversion efficiency (PCE) of 9.92 %. More importantly, this blend film's morphology is likely to be more conducive to the incorporation of the radical polymer additive, GDTA. This has resulted in a notable reduction in voltage loss, ultimately achieving a higher PCE of 11.55 % for the PDTBDT-F-FBT:Y6 based OSCs. This research uncovered a synergistic impact of backbone fluorination and the incorporation of radical polymer additives, which contributed to reducing the energy loss and enhancing the efficiency of OSCs from DTBDT-based polymer donors.

Direct Arylation Polycondensation‐Derived Polythiophene Achieves Over 16% Efficiency in Binary Organic Solar Cells via Tuning Aggregation and Miscibility

AbstractPolythiophenes are the most appealing donor materials in organic solar cells (OSCs) due to their simple chemical structures. However, the top‐performance polythiophenes are typically synthesized via Stille polycondensation, which is problematic due to significant toxicity and poor atom economy. By contrast, direct arylation polycondensation (DArP) is an eco‐friendly, and atom‐efficient alternative for synthesizing conjugated polymers, while the best efficiency for DArP‐derived polythiophenes is below 12%. This study reports a series of polythiophene‐based donors synthesized via DArP. Among these, PT4F‐Th reaches a power conversion efficiency (PCE) of 16.4%, which not only matches the current record for polythiophene‐based donor materials, but also marks the highest PCE achieved by DArP‐derived donors to date. The superior performance of PT4F‐Th is largely attributed to its optimal temperature‐dependent aggregation behavior and moderate miscibility with acceptors, along with the highest crystallinity among the candidates, resulting in the most favorable blend film morphology. This study underscores the significant potential of DArP‐derived polythiophenes in developing high‐performance and eco‐friendly OSCs.

The effect of polylactic acid-based blend films modified with various biodegradable polymers on the preservation of strawberries

Polylactic acid (PLA) has garnered much attention in the field of fruit and vegetable packaging. Despite its poor flexibility and water resistance, PLA film faces challenges in being used for strawberry storage and freshness preservation due to its inability to maintain flavor quality. In this study, a series of PLA-based modified films was produced by melt blending and extrusion cast processing with PLA as the main component, along with flexible biodegradable polyesters or polycarbonate as the secondary component. First, five different biodegradable polymers were used to investigate the effect of the flexibility and barrier properties of different dispersed phases on the morphology, mechanical properties, and water vapor barrier of PLA-based blend films. Next, the impact on the freshness of strawberries was assessed through examination of fruit color and weight, as well as the levels of O2 and CO2 in the packaging bags. The results showed that the size of the dispersed phase and interfacial bonding with PLA were the key factors determining the mechanical and barrier properties of the blend films. The PLA-polycaprolactone (PCL) blend showed the best compatibility among them, with PCL having the smallest dispersion size (D=0.58 µm), higher toughness than the other four PLA blends, and greater enhancement of PLA. Additionally, it exhibited a similar rate of quality loss in strawberry preservation compared to commercial PE. As a result, the color and luster were more completely preserved. The results of this study may help the future development of degradable plastics, to reduce environmental pollution.

Multi-component Copolymerized Donors enable Frozen Nano-morphology and Superior Ductility for Efficient Binary Organic Solar Cells.

Multi-component copolymerized donors (MCDs) have gained significant interest and have been rapidly developed in flexible organic solar cells (f-OSCs) in recent years. However, ensuring the power conversion efficiency (PCE) of f-OSCs while retaining ideal mechanical properties remains an enormous challenge. The fracture strain (FS) value of typical high-efficiency blend films is generally less than 8 %, which is far from the application standards of wearable photovoltaic devices. Therefore, we developed a series of novel MCDs after meticulous molecular design. Among them, the consistent MCD backbone and end-capped functional group formed a highly conjugated molecular plane, and the solubilization and mechanical properties were effectively optimized by modifying the proportion of solubilized alkyl chains. Consequently, due to the formation of entangled structures with a frozen blend film morphology considerably improved the high ductility of the active layer, P10.8/P20.2-TCl exhibited efficient PCE in rigid (18.53 %) and flexible (17.03 %) OSCs, along with excellent FS values (16.59 %) in pristine films, meanwhile, the outstanding FS values of 25.18 % and 12.3 % were achieved by P10.6/P20.4-TCl -based pristine and blend films, respectively, which were one of the highest records achieved by end-capped MCD-based binary OSCs, demonstrating promising application to synchronize the realization of high-efficiency and mechanically ductile flexible OSCs.

Controlling vertical phase separation and crystallization via solvent synergy strategy to empower layer-by-layer processed organic solar cells

The novel sequential layer-by-layer (LbL) processed organic solar cells (OSCs) have attracted continuous attention due to their advantages of ideal vertical phase separation, efficient charge transport and collection, and potentiality for large-scale production from laboratory to factory. Herein, a solvent synergy strategy is put forward to control morphology, crystallization and vertical phase distribution of blend films, which means the donor PM6 and acceptor Y6 treated by high/low boiling point solvents are fabricated using LbL solution process, respectively. Based on device with a configuration of ITO/ZnO/PM6:Y6/MoO3/Ag, OSCs derived from the solvent synergy strategy can obtain a remarkable power conversion efficiency (PCE) up to 15.03%, which is comparable to that of the bulk heterojunction devices prepared by conventional one-step solution method. This impressive result provides an insightful understanding of phase segregation and crystalllization in LbL processed OSCs assisted by the solvent synergy strategy. It lays the foundation for fabrication and optimization of high-performance, large-area OSCs in industrial production.

Polymerizing M-Series Acceptors for Efficient Polymer Solar Cells: Effect of the Molecular Shape.

Currently, high-performance polymerized small-molecule acceptors (PSMAs) based on ADA-type SMAs are still rare and greatly demanded for polymer solar cells (PSCs). Herein, two novel regioregular PSMAs (PW-Se and PS-Se) are designed and synthesized by using centrosymmetric (linear-shaped) and axisymmetric (banana-shaped) ADA-type SMAs as the main building blocks, respectively. It is demonstrated that photovoltaic performance of the PSMAs can be significantly improved by optimizing the configuration of ADA-type SMAs. Compared to the axisymmetric SMA-based polymer (PS-Se), PW-Se using a centrosymmetric SMA as the main building block exhibits better backbone coplanarity thereby resulting in bathochromically shifted absorption with a higher absorption coefficient, tighter interchain π-π stacking, and more favorable blend film morphology. As a result, enhanced and more-balanced charge transport, better exciton dissociation, and reduced charge recombination are achieved for PW-Se-based devices with PM6 as polymer donor. Benefiting from these positive factors, the optimal PM6:PW-Se-based device exhibits a higher power conversion efficiency (PCE) of 15.65% compared to the PM6:PS-Se-based device (8.90%). Furthermore, incorporation of PW-Se as a third component in the binary active layer of PM6:M36 yields ternary devices with an outstanding PCE of 18.0%, which is the highest value for PSCs based on ADA-type SMAs, to the best of the knowledge.

Reconstructing the 3D Coordinates of Guest:Host OLED Blends with Single Atom Resolution.

The performance of electronic and semiconductor devices is critically dependent on the distribution of guest molecules or atoms in a host matrix. One prominent example is that of organic light-emitting diode (OLED) displays containing phosphorescent emitters, now ubiquitous in handheld devices and high-end televisions. In such OLEDs the phosphorescent guest [normally an iridium(III)-based complex] is typically blended into a host matrix, and charge injection and transport, exciton formation and decay, and hence overall device performance are governed by the distribution of the emissive guest in the host. Here high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is used with depth sectioning to reconstruct the 3D distribution of emissive iridium(III) complexes, fac-tris(2-phenylpyridine)iridium(III) [Ir(ppy)3], blended into the amorphous host material, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), by resolving the position of each single iridium(III) ion. It is found that most Ir(ppy)3 complexes are clustered with at least one other, even at low concentrations, and that for films of 20wt.% Ir(ppy)3 essentially all the complexes are interconnected. The results validate the morphology of blend films created using molecular dynamics simulations which mimic the evaporation film-forming process and are also consistent with the experimentally measured charge transport and photophysical properties.

A Three-Dimensional Non-Fullerene Acceptor with Contorted Hexabenzocoronene and Perylenediimide for Organic Solar Cells.

Although fullerene derivatives such as [6,6]-phenyl-C61/C71-butyric acid methyl ester (PC61BM/PC71BM) have dominated the the photoactive acceptor materials in bulk heterojunction organic solar cells (OSCs) for decades, they have several drawbacks such as weak absorption, limited structural tunability, prone to aggregation, and high costs of production. Constructing non-fullerene small molecules with three-dimensional (3D) molecular geometry is one of the strategies to replace fullerenes in OSCs. In this study, a 3D molecule, contorted hexa-cata-hexabenzocoronene tetra perylenediimide (HBC-4-PDI), was designed and synthesized. HBC-4-PDI shows a wide and strong light absorption in the whole UV-vis region as well as suitable energy levels as an acceptor for OSCs. More importantly, the 3D construction effectively reduced the self-aggregation of c-HBC, leading to an appropriate scale phase separation of the blend film morphology in OSCs. A preliminary power conversion efficiency of 2.70 % with a champion open-circuit voltage of 1.06 V was obtained in OSCs with HBC-4-PDI as the acceptor, which was the highest among the previously reported OSCs based on c-HBC derivatives. The results indicated that HBC-4-PDI may serve as a good non-fullerene acceptor for OSCs.

Morphology optimization induced by a highly volatile solid additive contributes to efficient organic solar cells with enhanced photostability

The morphology of the active layer plays a crucial role in the device performance and stability of organic solar cells (OSCs). To obtain the optimized blend film morphology, numerous solvent additives have been developed and utilized. Nevertheless, the commonly used high boiling point solvent additives have strict volume control and residual problems, which are not conducive to the development of OSCs. To alter the situation, it is urgent to develop highly volatile additives to minimize the unfavorable effect. Here, a volatile aromatic small molecule, benzoylacetate (BA), is used as a solid additive to control the morphology of the active layer during the post-treatment procedure. More importantly, BA has an apparent positive interaction with Y6, leading to more favorable molecular arrangement in the blend film and enhanced charge transfer properties. Finally, the BA-treated PM6:Y6 device exhibits improved device performance and photostability. Moreover, BA could be used as a universal solid additive for different OSC systems. Specifically, a superior PCE of 18.5 % is achieved in BA-processed PM6:L8-BO binary system with good photostability. Our work demonstrates an approach of applying a volatile solid additive to improve the device performance and photostability.

Highly-Efficient 2D Nonfullerene Acceptors Enabled by Subtle Molecular Tailoring Engineering.

The conjugate expansion of nonfullerene acceptors is considered to be a promising approach for improving organic photovoltaic performance because of its function in tuning morphological structure and molecular stacking behavior. In this work, two nonfullerene acceptors are designed and synthesized using a 2D π-conjugate expansion strategy, thus enabling the construction of highly-efficient organic solar cells (OSCs). Compared with YB2B (incorporating dibromophenanthrene on the quinoxaline-fused core), YB2T (incorporating dibromobenzodithiophene on the quinoxaline-fused core) has red-shifted spectral absorption and better charge transport properties. Moreover, the more orderly and tightly intermolecular stacking of YB2T provides the possibility of forming a more suitable phase separation morphology in blend films. Through characterization and analysis, the YB2T-based blend film is found to have higher exciton dissociation efficiency and less charge recombination. Consequently, the power conversion efficiency (PCE) of 17.05% is achieved in YB2T-based binary OSCs, while YB2B-based devices only reached 10.94%. This study demonstrates the significance of the aromatic-ring substitution strategy for regulating the electronic structure and aggregation behavior of 2D nonfullerene acceptors, facilitating the development of devices with superior photovoltaic performance.

Halogenated Nonfused Ring Electron Acceptor for Organic Solar Cells with a Record Efficiency of over 17.

Three nonfused ring electron acceptors (NFREAs), namely, 3TT-C2-F, 3TT-C2-Cl, and 3TT-C2, are purposefully designed and synthesized with the concept of halogenation. The incorporation of F or/and Cl atoms into the molecular structure (3TT-C2-F and 3TT-C2-Cl) enhances the π-π stacking, improves electron mobility, and regulates the nanofiber morphology of blend films, thus facilitating the exciton dissociation and charge transport. In particular, blend films based on D18:3TT-C2-F demonstrate a high charge mobility, an extended exciton diffusion distance, and a well-formed nanofiber network. These factors contribute to devices with a remarkable power conversion efficiency of 17.19%, surpassing that of 3TT-C2-Cl (16.17%) and 3TT-C2 (15.42%). To the best of knowledge, this represents the highest efficiency achieved in NFREA-based devices up to now. These results highlight the potential of halogenation in NFREAs as a promising approach to enhance the performance of organic solar cells.

Enhancing Photovoltaic Performance of Nonfused‐Ring Electron Acceptors via Asymmetric End‐Group Engineering and Noncovalently Conformational Locks

Comprehensive SummaryBy employing the asymmetric end‐group engineering, an asymmetric nonfused‐ring electron acceptor (NFREA) was designed and synthesized. Compared with the symmetric analogs (NoCA‐17 and NoCA‐18), NoCA‐19 possesses broader light absorption range, more coplanar π‐conjugated backbone, and appropriate crystallinity according to the experimental and theoretical results. The organic solar cells based on J52:NoCA‐19 exhibited a power conversion efficiency as high as 12.26%, which is much higher than those of J52:NoCA‐17 (9.50%) and J52:NoCA‐18 (11.77%), mainly due to more efficient exciton dissociation, better and balanced charge mobility, suppressed recombination loss, shorter charge extraction time, longer charge carrier lifetimes, and more favorable blend film morphology. These findings demonstrate the great potential of asymmetric end‐group engineering in exploring low‐cost and high‐performance NFREAs.

Central Core Substitutions and Film-Formation Process Optimization Enable Approaching 19% Efficiency All-Polymer Solar Cells.

Molecular interactions and film-formation processes greatly impact the blend film morphology and device performances of all-polymer solar cells (all-PSCs). Molecular structure, such as the central cores of polymer acceptors, would significantly influence this process. Herein, the central core substitutions of polymer acceptors are adjusted and three quinoxaline (Qx)-fused-core-based materials, PQx1, PQx2, and PQx3 are synthesized. The molecular aggregation ability and intermolecular interaction are systematically regulated, which subsequently influence the film-formation process and determine the resulting blend film morphology. As a result, PQx3, with favorable aggregation ability and moderate interaction with polymer donor PM6, achieves efficient all-PSCs with a high power conversion efficiency (PCE) of 17.60%, which could be further improved to 18.06% after carefully optimizing device annealing and interface layer. This impressive PCE is one of the highest values for binary all-PSCs based on the classical polymer donor PM6. PYF-T-o is also involved in promoting light utilization, and the resulting ternary device shows an impressive PCE of 18.82%. In addition, PM6:PQx3-based devices exhibit high film-thickness tolerance, superior stability, and considerable potential for large-scale devices (16.23% in 1 cm2 device). These results highlight the importance of structure optimization of polymer acceptors and film-formation process control for obtaining efficient and stable all-PSCs.

Introducing thiazole units into small-molecule acceptors for efficient non-fullerene organic solar cells

The end-group modification engineering has been widely applied in non-fullerene acceptors (NFAs) to achieve high-performance organic solar cells (OSCs). Herein, we designed and synthesized a series of small-molecule acceptors (SMAs), namely ODTz-γ, ODTz-m, DTTz-γ and DTTz-m, which containing the electron-withdrawing thiazole units on the end groups at different position. These SMAs not only exhibited strong and broad absorption region from 500 nm to 900 nm, identical band gaps, but also the similar energy levels, indicating the position of thiazole units have trivial effect on their absorbance and energy levels. OSCs were fabricated by integrating an electron-donating polymer PBDB-T with these resultant electron-accepting materials. Devices based on ODTz-γexhibited an obviously higher power conversion efficiency over 12.0%, which outperformed those of obtained from devices based on other SMAs. Further characterization of the devices revealed that introducing the thiazole units into the γ position of end groups can enhance the charge transport mobility, suppress recombination, and improve the blend film morphology.

Effects of Conjugation Spacers in Diketopyrrolopyrrole-Based Copolymers for All-Polymer-Based Photodiodes

The selection of the π-conjugation spacers in semi-conducting polymer backbone is one of the important factors for determining the optoelectrical and morphological properties in organic photodiodes. To study the effects of π-conjugation spacers in donor–acceptor (D-A)-type alternating copolymers on their device performances in all-polymer-based photodiodes (all-PPDs), a series of diketopyrrolopyrrole (DPP)-based copolymers as polymer donors (PDs) were designed and synthesized. In detail, three different π-conjugation spacers, thiophene (T for P1), thienothiophene (TT for P2), and bithiophene (BT for P3), were incorporated into the DPP-based copolymer structures. Interestingly, all-PPDs based on the series of P1–P3 as PDs and N2200 as a polymer acceptor (PA) exhibited totally distinct device performances in terms of external quantum efficiency (EQE), dark current density (JD), and ideal detectivity (D*). The P1-based device showed suppressed JD (6.1 × 10−11 A/cm2 at −1 V) compared to those of the P2- and P3-based devices due to the lower lying of the highest occupied molecular orbital (HOMO) level of P1. However, the P3-based all-PPD showed higher EQE (16% at 630 nm wavelength and −1 V) compared to those of the P1- and P2-based devices. And, it mainly originated from the better molecular packing and final blend film morphology, as confirmed by morphological analyses.

New wide bandgap conjugated D-A copolymers based on Benzo[d]thiazole for efficient photovoltaics

Two wide bandgap copolymers based on benzo[d]thiazole unit, named PBTz-F and PBTz-Cl, containing benzo[1,2-b:4,5-b′]dithiophene (BDT) as electron donor units are developed. The resulting polymers lower the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels via substituting halogen atoms (fluorine or chlorine atoms) on the thiophene side chain of the BDT unit. However, the chlorine atom in the copolymers has a stronger capacity to downshift energy levels than the fluorine atom. PBTz-Cl:Y6-BO-based OSC delivers a higher PCE of 12.36% with simultaneously enhanced VOC of 0.90 V, JSC of 22.78 mA cm−2, and FF of 0.61 when compared to that based on PBTz-F:Y6-BO (PCE = 11.38%, JSC = 22.48 mA cm−2, VOC = 0.88 V, and FF = 0.58) due to its stronger absorption, higher charge mobilities, deeper HOMO energy level, and favorable blend film morphology. These results emphasized that chlorination is a practical strategy to obtain high PCE and BTz-based polymers are potential donor candidates for high-performance OSCs.

Ternary Organic Solar Cells with Power Conversion Efficiency Approaching 15% by Fine-Selecting the Third Component.

Nonfullerene acceptors with mediate bandgap play a crucial role in ternary devices as the third component, further boosting the performance of organic solar cells (OSCs). Herein, three F-series acceptors (F-H, F-Cl, and F-2Cl) with mediate bandgap are selected and introduced into the PM6:BDT-Br binary system as third component to find the detailed influence of end groups with chlorine (Cl) atom substitution on the performance of ternary organic solar cells. Due to the increased substitution of Cl atoms on the end groups, F-Cl and F-2Cl as guest acceptors reveal a superior ability to regulate the morphology of blend films, contributing to the ordered packing properties and high crystallinity. As a result, F-Cl and F-2Cl based ternary OSCs achieve significantly improved PCEs of 13.89% and 14.67%, respectively, compared with the binary devices (12.70%). On the contrary, F-H without Cl atom displays a poor compatibility with the host system, resulting in an inferior ternary device with a low PCE of 10.79%. This work indicates that F-series acceptors with mediate bandgap are a promising class of third component for high-performance ternary OSCs. And introducing more Cl atoms substitution on the end groups, especially F-2Cl, will own a broad applicability for other binary devices.

Efficient and Scalable Large‐Area Organic Solar Cells by Asymmetric Nonfullerene Acceptors Based on 9H‐Indeno[1,2‐b]pyrazine‐2,3,8‐Tricarbonitrile

AbstractIt remains challenging to fabricate efficient, scalable large‐area organic solar cells (OSCs) owing to the unfavorable morphology of photoactive blend films. To address this challenge, two asymmetric nonfullerene acceptors (NFAs) IPC1CN‐BBO‐IC2F and IPC1CN‐BBO‐IC2Cl are synthesized, where 12,13‐bis(2‐butyloctyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2′“,3′”:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno‐[3,2‐b]indole (BBO) is the molecular core, and two types of end groups are appended to its ends, namely the 9H‐indeno[1,2‐b]pyrazine‐2,3,8‐tricarbonitrile (IPC1CN) end group and one of 2‐(5,6‐dihalo‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile end groups (IC2F or IC2Cl). These NFAs facilitate effective tuning of light absorption and energy levels, offer high carrier mobilities, and allow for the formation of appropriate morphologies. Note that these benefits apply even to large‐area devices, unlike typical Y6‐based NFAs. In addition, a random copolymer PM6‐PBDBT(55) is synthesized and its energy levels are optimally matched with those of the asymmetric NFAs. The blade‐coated 1 cm2‐area OSCs based on PM6‐PBDBT(55):IPC1CN‐BBO‐IC2Cl exhibit a PCE of 14.12%, which is higher than that of PM6‐PBDBT(55)‐IPC1CN‐BBO‐IC2F‐based OSCs. More importantly, the PM6‐PBDBT(55):IPC1CN‐BBO‐IC2Cl‐based large‐area (58.50 cm2) modules yield an impressive PCE of 11.28% with a small cell‐to‐module loss in fill factor. These results suggest that a combination of the asymmetric molecular design using the IPC1CN group and the terpolymer strategy will pave a new path for fabricating highly efficient and scalable large‐area OSCs.

Revealing the Molecular Weight Effect on Highly Efficient Polythiophene Solar Cells.

Polythiophenes (PTs) are promising electron donors in organic solar cells (OSCs) due to their simple structures and excellent synthetic scalability. Benefiting from the rational molecular design, the power conversion efficiency (PCE) of PT solar cells has been greatly improved. Herein, five batches of the champion PT (P5TCN-F25) with molecular weights ranging from 30 to 87 kg mol-1 were prepared, and the effect of the molecular weight on the blend film morphology and photovoltaic performance of PT solar cells was systematically investigated. The results showed that the PCEs of the devices improved first and then maintained a high value with the increase of molecular weight, and the highest PCE of 16.7% in binary PT solar cells was obtained. Further characterizations revealed that the promotion in photovoltaic performance mainly comes from finer phase separation structures and more compact molecular packing in the blend film. The best device stabilities were also achieved by polymers with high molecular weights. Overall, this study highlights the importance of optimizing the molecular weight for PTs and offers directions to further improve the PCE of PT solar cells.