A Synergetic Effect of Molecular Weight and Fluorine in All‐Polymer Solar Cells with Enhanced Performance

A synergetic effect of molecular weight (M_n) and fluorine (F) on the performance of all‐polymer solar cells (all‐PSCs) is comprehensively investigated by tuning the M_n of the acceptor polymer poly((N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl)‐alt‐5,5′‐(2,2′‐bithiophene)) (P(NDI2OD‐T2)) and the F content of donor polymer poly(2,3‐bis‐(3‐octyloxyphenyl)quinoxaline‐5,8‐dyl‐alt‐thiophene‐2,5‐diyl). Both M_n and F variations strongly influence the charge transport properties and morphology of the blend films, which have a significant impact on the photovoltaic performance of all‐PSCs. In particular, the effectiveness of high M_n in increasing power conversion efficiency (PCE) can be greatly improved by the devices based on optimum F content, reaching a PCE of 7.31% from the best all‐PSC combination. These findings enable us to further understand the working principles of all‐PSCs with a view on achieving even higher power conversion efficiency in the future.     

The Impact of Sequential Fluorination of π‐Conjugated Polymers on Charge Generation in All‐Polymer Solar Cells

The performance of all‐polymer solar cells (all‐PSCs) is often limited by the poor exciton dissociation process. Here, the design of a series of polymer donors ( P1 – P3 ) with different numbers of fluorine atoms on their backbone is presented and the influence of fluorination on charge generation in all‐PSCs is investigated. Sequential fluorination of the polymer backbones increases the dipole moment difference between the ground and excited states (Δµ_ge) from P1 (18.40 D) to P2 (25.11 D) and to P3 (28.47 D). The large Δµ_ge of P3 leads to efficient exciton dissociation with greatly suppressed charge recombination in P3 ‐based all‐PSCs. Additionally, the fluorination lowers the highest occupied molecular orbital energy level of P3 and P2 , leading to higher open‐circuit voltage (V_OC). The power conversion efficiency of the P3 ‐based all‐PSCs (6.42%) outperforms those of the P2 and P1 (5.00% and 2.65%)‐based devices. The reduced charge recombination and the enhanced polymer exciton lifetime in P3 ‐based all‐PSCs are confirmed by the measurements of light‐intensity dependent short‐circuit current density (J_SC) and V_OC, and time‐resolved photoluminescence. The results provide reciprocal understanding of the charge generation process associated with Δµ_ge in all‐PSCs and suggest an effective strategy for designing π‐conjugated polymers for high performance all‐PSCs.     

Ambient Processable and Stable All‐Polymer Organic Solar Cells

In this work, the way in which ambient moisture impacts the photovoltaic performance of conventional PCBM and emerging polymer acceptor–based organic solar cells is examined. The device performance of two representative p‐type polymers, PBDB‐T and PTzBI, blended with either PCBM or polymeric acceptor N2200, is systemically investigated. In both cases, all‐polymer photovoltaic devices processed from high‐humidity ambient conditions exhibit significantly enhanced moisture‐tolerance compared to their polymer–PCBM counterparts. The impact of moisture on the blend film morphology and electronic properties of the electron acceptor (N2200 vs PCBM), which results in different recombination kinetics and electron transporting properties, are further compared. The impact of more comprehensive ambient conditions (moisture, oxygen, and thermal stress) on the long‐term stability of the unencapsulated devices is also investigated. All‐polymer solar cells show stable performance for long periods of storage time under ambient conditions. The authors believe that these findings demonstrate that all‐polymer solar cells can achieve high device performance with ambient processing and show excellent long‐term stability against oxygen and moisture, which situate them in an advantageous position for practical large‐scale production of organic solar cells.     

Achieving an Efficiency Exceeding 10% for Fullerene‐based Polymer Solar Cells Employing a Thick Active Layer via Tuning Molecular Weight

Recently, the influence of molecular weight (M_n) on the performance of polymer solar cells (PSCs) is widely investigated. However, the dependence of optimal thickness of active layer for PSCs on M_n is not reported yet, which is vital to the solution printing technology. In this work, the effect of M_n on the efficiency and especially optimal thickness of the active layer for PBTIBDTT‐S‐based PSCs is systematically studied. The device efficiency improves significantly as the M_n increases from 12 to 38 kDa, and a remarkable efficiency of 10.1% is achieved, which is among the top efficiencies of wide‐bandgap polymer:fullerene PSCs. Furthermore, the optimal thickness of the active layer is also greatly increased from 62 to 210 nm with increased M_n. Therefore, a device employing a thick (>200 nm) active layer with power conversion efficiency exceeding 10% is achieved by manipulating M_n. This exciting result is attributed to both the improved crystallinity, thus hole mobility, and preferable polymer orientation, thus morphology of active layer. These findings, for the first time, highlight the significant impact of M_n on the optimal thickness of active layer for PSCs and provide a facile way to further improve the performance of PSCs employing a thick active layer.     

Precise Manipulation of Multilength Scale Morphology and Its Influence on Eco‐Friendly Printed All‐Polymer Solar Cells

Significant efforts have lead to demonstrations of nonfullerene solar cells (NFSCs) with record power conversion efficiency up to ≈13% for polymer:small molecule blends and ≈9% for all‐polymer blends. However, the control of morphology in NFSCs based on polymer blends is very challenging and a key obstacle to pushing this technology to eventual commercialization. The relations between phases at various length scales and photovoltaic parameters of all‐polymer bulk‐heterojunctions remain poorly understood and seldom explored. Here, precise control over a multilength scale morphology and photovoltaic performance are demonstrated by simply altering the concentration of a green solvent additive used in blade‐coated films. Resonant soft X‐ray scattering is used to elucidate the multiphasic morphology of these printed all‐polymeric films and complements with the use of grazing incidence wide‐angle X‐ray scattering and in situ spectroscopic ellipsometry characterizations to correlate the morphology parameters at different length scales to the device performance metrics. Benefiting from the highest relative volume fraction of small domains, additive‐free solar cells show the best device performance, strengthening the advantage of single benign solvent approach. This study also highlights the importance of high volume fraction of smallest domains in printed NFSCs and organic solar cells in general.     

A Chlorinated Donor Polymer Achieving High-Performance Organic Solar Cells with a Wide Range of Polymer Molecular Weight

In the field of non-fullerene organic solar cells (OSCs), compared to the rapid development of non-fullerene acceptors, the progress of high-performance donor polymers is relatively slow. The property and performance of donor polymers in OSCs are often sensitive to the molecular weight of the polymers. In this study, a chlorinated donor polymer named D18-Cl is reported, which can achieve high performance with a wide range of polymer molecular weight. The devices based on D18-Cl show a higher open-circuit voltage (V_OC) due to the slightly deeper energy levels and an outstanding short-circuit current density (J_SC) owing to the appropriate long periods of blend films and less ([6,6]-phenyl-C71-butyric acid methyl ester) (PC₇₁BM) in mixed domains, leading to the higher efficiency of 17.97% than those of the D18-based devices (17.21%). Meanwhile, D18-Cl can achieve high efficiencies (17.30–17.97%) when its number-averaged molecular weight (M_n) is ranged from 45 to 72 kDa. In contrast, the D18-based devices only exhibit relatively high efficiencies in a narrow M_n range of ≈70 kDa. Such property and performance make D18-Cl a promising donor polymer for scale-up and low-cost production.     

Side Chain Optimization of Naphthalenediimide–Bithiophene‐Based Polymers to Enhance the Electron Mobility and the Performance in All‐Polymer Solar Cells

Tuning the side chains of conjugated polymers is a simple, yet effective strategy for modulating their structural and electrical properties, but their impact on n‐type conjugated polymers has not been studied extensively, particularly in the area of all‐polymer solar cells (all‐PSCs). Herein, the effects of side chain engineering of P(NDI2OD‐T2) polymer (also known as Polyera Activink N2200) are investigated, which is the most widely used n‐type polymer in all‐PSCs and organic field‐effect transistors (OFETs), on their structural and electronic properties. A series of naphthalenediimide‐bithiophene‐based copolymers (P(NDIR‐T2)) is synthesized, with different side chains (R) of 2‐hexyldecyl (2‐HD), 2‐octyldodecyl (2‐OD), and 2‐decyltetradecyl (2‐DT). The P(NDI2HD‐T2) exhibits more noticeable crystalline behaviors than P(NDI2OD‐T2) and P(NDI2DT‐T2), thereby facilitating superior 3D charge transport. For example, the P(NDI2HD‐T2) shows the highest OFET electron mobility (1.90 cm² V^?1 s^?1). Also, a series of all‐PSCs is produced using different electron donors of PTB7‐Th, PTB7, and PPDT2FBT. The P(NDI2HD‐T2) based all‐PSCs produce much higher power conversion efficiency (PCE) irrespective of the electron donors. In particular, the PTB7‐Th:P(NDI2HD‐T2) forms highly ordered, strong face‐on interchain stackings, and has better intermixed bulk‐heterojunction morphology, producing the highest PCE of 6.11% that has been obtained by P(NDIR‐T2) based all‐PSCs to date.     

Correlated Donor/Acceptor Crystal Orientation Controls Photocurrent Generation in All‐Polymer Solar Cells

New polymers with high electron mobilities have spurred research in organic solar cells using polymeric rather than fullerene acceptors due to their potential of increased diversity, stability, and scalability. However, all‐polymer solar cells have struggled to keep up with the steadily increasing power conversion efficiency of polymer:fullerene cells. The lack of knowledge about the dominant recombination process as well as the missing concluding picture on the role of the semi‐crystalline microstructure of conjugated polymers in the free charge carrier generation process impede a systematic optimization of all‐polymer solar cells. These issues are examined by combining structural and photo‐physical characterization on a series of poly(3‐hexylthiophene) (donor) and P(NDI2OD‐T2) (acceptor) blend devices. These experiments reveal that geminate recombination is the major loss channel for photo‐excited charge carriers. Advanced X‐ray and electron‐based studies reveal the effect of chloronaphthalene co‐solvent in reducing domain size, altering domain purity, and reorienting the acceptor polymer crystals to be coincident with those of the donor. This reorientation correlates well with the increased photocurrent from these devices. Thus, efficient split‐up of geminate pairs at polymer/polymer interfaces may necessitate correlated donor/acceptor crystal orientation, which represents an additional requirement compared to the isotropic fullerene acceptors.     

Self‐Doping Fullerene Electrolyte‐Based Electron Transport Layer for All‐Room‐Temperature‐Processed High‐Performance Flexible Polymer Solar Cells

To achieve high‐performance large‐area flexible polymer solar cells (PSCs), one of the challenges is to develop new interface materials that possess a thermal‐annealing‐free process and thickness‐insensitive photovoltaic properties. Here, an n‐type self‐doping fullerene electrolyte, named PCBB‐3N‐3I, is developed as electron transporting layer (ETL) for the application in PSCs. PCBB‐3N‐3I ETL can be processed at room temperature, and shows excellent orthogonal solvent processability, substantially improved conductivity, and appropriate energy levels. PCBB‐3N‐3I ETL also functions as light‐harvesting acceptor in a bilayer solar cell, contributing to the overall device performance. As a result, the PCBB‐3N‐3I ETL‐based inverted PSCs with a PTB7‐Th:PC₇₁BM photoactive layer demonstrate an enhanced power conversion efficiency (PCE) of 10.62% for rigid and 10.04% for flexible devices. Moreover, the device avoids a thermal annealing process and the photovoltaic properties are insensitive to the thickness of PCBB‐3N‐3I ETL, yielding a PCE of 9.32% for the device with thick PCBB‐3N‐3I ETL (61 nm). To the best of one's knowledge, the above performance yields the highest efficiencies for the flexible PSCs and thick ETL‐based PSCs reported so far. Importantly, the flexible PSCs with PCBB‐3N‐3I ETL also show robust bending durability that could pave the way for the future development of high‐performance flexible solar cells.     

Improved All‐Polymer Solar Cell Performance by Using Matched Polymer Acceptor

By the introduction of different building blocks and side‐chains, a series of donor–acceptor type polymer acceptors containing naphthalene diimide have been successfully prepared. The theoretical and experimental results show that the molecular design effectively tunes the energy levels, solubility, and coplanarity of the acceptor polymers. The intermolecular packing, which has been considered as a key factor in the bulk heterojunction morphology, has been adjusted by changing the coplanarity. As a result of improved morphology and fine‐tuned energy levels, a power conversion efficiency of 6.0% has been demonstrated for the optimized devices, which is among the highest‐efficiencies for reported all‐polymer solar cells. The improved device performance may be attributed to the resemble crystallinity of the donor/acceptor polymers, which can lead to the optimal phase separation morphology balancing both charge transfer and transport.     

The Effect of Poly(3‐hexylthiophene) Molecular Weight on Charge Transport and the Performance of Polymer:Fullerene Solar Cells

The time‐of‐flight method has been used to study the effect of P3HT molecular weight (M_n = 13–121 kDa) on charge mobility in pristine and PCBM blend films using highly regioregular P3HT. Hole mobility was observed to remain constant at 10^?4 cm²V^?1s^?1 as molecular weight was increased from 13–18 kDa, but then decreased by one order of magnitude as molecular weight was further increased from 34–121 kDa. The decrease in charge mobility observed in blend films is accompanied by a change in surface morphology, and leads to a decrease in the performance of photovoltaic devices made from these blend films.     

Shift of the Branching Point of the Side‐Chain in Naphthalenediimide (NDI)‐Based Polymer for Enhanced Electron Mobility and All‐Polymer Solar Cell Performance

The branching point of the side‐chain of naphthalenediimide (NDI)‐based conjugated polymers is systematically controlled by incorporating four different side‐chains, i.e., 2‐hexyloctyl (P(NDI1‐T)), 3‐hexylnonyl (P(NDI2‐T)), 4‐hexyldecyl (P(NDI3‐T)), and 5‐hexylundecyl (P(NDI4‐T)). When the branching point is located farther away from the conjugated backbones, steric hindrance around the backbone is relaxed and the intermolecular interactions between the polymer chains become stronger, which promotes the formation of crystalline structures in thin film state. In particular, thermally annealed films of P(NDI3‐T) and P(NDI4‐T), which have branching points far away from the backbone, possess more‐developed bimodal structure along both the face‐on and edge‐on orientations. Consequently, the field‐effect electron mobilities of P(NDIm‐T) polymers are monotonically increased from 0.03 cm² V⁻¹ s⁻¹ in P(NDI1‐T) to 0.22 cm² V⁻¹ s⁻¹ in P(NDI4‐T), accompanied by reduced activation energy and contact resistance of the thin films. In addition, when the series of P(NDIm‐T) polymers is applied in all‐polymer solar cells (all‐PSCs) as electron acceptor, remarkably high‐power conversion efficiency of 7.1% is achieved along with enhanced current density in P(NDI3‐T)‐based all‐PSCs, which is mainly attributed to red‐shifted light absorption and enhanced electron‐transporting ability.     

A Cross‐Linkable Donor Polymer as the Underlying Layer to Tune the Active Layer Morphology of Polymer Solar Cells

For polymer solar cells (PSCs) with conventional configuration, the vertical composition profile of donor:acceptor in active layer is detrimental for charge carrier transporting/collection and leads to decreased device performance. A cross‐linkable donor polymer as the underlying morphology‐inducing layer (MIL) to tune the vertical composition distribution of donor:acceptor in the active layer for improved PSC device performance is reported. With poly(thieno[3,4‐b]‐thiophene/benzodithiophene):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PTB7:PC₇₁BM) as the active layer, the MIL material, PTB7‐TV , is developed by attaching cross‐linkable vinyl groups to the side chain of PTB7. PSC device with PTB7‐TV layer exhibits a power conversion efficiency (PCE) of 8.55% and short‐circuit current density (J_SC) of 15.75 mA cm^?2, in comparison to PCE of 7.41% and J_SC of 13.73 mA cm^?2 of the controlled device. The enhanced device performance is ascribed to the much improved vertical composition profile and reduced phase separation domain size in the active layer. These results demonstrate that cross‐linked MIL is an effective strategy to improve photovoltaic performance of conventional PSC devices.     

Impact of Nonfullerene Molecular Architecture on Charge Generation,Transport, and Morphology in PTB7‐Th‐Based Organic Solar Cells

Despite the rapid development of nonfullerene acceptors (NFAs), the fundamental understanding on the relationship between NFA molecular architecture, morphology, and device performance is still lacking. Herein, poly[[4,8‐bis[5‐(2‐ethylhexyl)thiophene‐2‐yl]benzo[1,2‐b:4,5‐b0]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]‐thieno[3,4‐b]thiophenediyl]] (PTB7‐Th) is used as the donor polymer to compare an NFA with a 3D architecture (SF‐PDI4) to a well‐studied NFA with a linear acceptor–donor–acceptor (A–D–A) architecture (ITIC). The data suggest that the NFA ITIC with a linear molecular structure shows a better device performance due to an increase in short‐circuit current ( J_sc) and fill factor (FF) compared to the 3D SF‐PDI4. The charge generation dynamics measured by femtosecond transient absorption spectroscopy (TAS) reveals that the exciton dissociation process in the PTB7‐Th:ITIC films is highly efficient. In addition, the PTB7‐Th:ITIC blend shows a higher electron mobility and lower energetic disorder compared to the PTB7‐Th:SF‐PDI4 blend, leading to higher values of J_sc and FF. The compositional sensitive resonant soft X‐ray scattering (R‐SoXS) results indicate that ITIC molecules form more pure domains with reduced domain spacing, resulting in more efficient charge transport compared with the SF‐PDI4 blend. It is proposed that both the molecular structure and the corresponding morphology of ITIC play a vital role for the good solar cell device performance.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

Rationally Designed Donor–Acceptor Random Copolymers with Optimized Complementary Light Absorption for Highly Efficient All‐Polymer Solar Cells

Most of the high‐performance all‐polymer solar cells (all‐PSCs) reported to date are based on polymer donor and polymer acceptor pairs with largely overlapped light absorption properties, which seriously limits the efficiency of all‐PSCs. This study reports the development of a series of random copolymer donors possessing complementary light absorption with the naphthalenediimide‐based polymer acceptor P(NDI2HD‐T2) for highly efficient all‐PSCs. By controlling the molar ratio of the electron‐rich benzodithiophene (BDTT) and electron‐deficient fluorinated‐thienothiophene (TT‐F) units, a series of polymer donors with BDTT:TT‐F ratios of 1:1 (P1), 3:1 (P2), 5:1 (P3), and 7:1 (P4) are prepared. The synthetic control of polymer composition allows for precise tuning of the light absorption properties of these new polymer donors, enabling optimization of light absorption properties to complement those of the P(NDI2HD‐T2) acceptor. Copolymer P1 is found to be the optimal polymer donor for the fullerene‐based solar cells due to its high light absorption, whereas the highest power conversion efficiency of 6.81% is achieved for the all‐PSCs with P3, which has the most complementary light absorption with P(NDI2HD‐T2).     

High‐Performance All‐Polymer Photoresponse Devices Based on Acceptor–Acceptor Conjugated Polymers

Three acceptor–acceptor (A–A) type conjugated polymers based on isoindigo and naphthalene diimide/perylene diimide are designed and synthesized to study the effects of building blocks and alkyl chains on the polymer properties and performance of all‐polymer photoresponse devices. Variation of the building blocks and alkyl chains can influence the thermal, optical, and electrochemical properties of the polymers, as indicated by thermogravimetric analysis, differential scanning calorimetry, UV–vis, cyclic voltammetry, and density functional theory calculations. Based on the A–A type conjugated polymers, the most efficient all‐polymer photovoltaic cells are achieved with an efficiency of 2.68%, and the first all‐polymer photodetectors are constructed with high responsivity (0.12 A W^?1) and detectivity (1.2 × 10¹² Jones), comparable to those of the best fullerene based organic photodetectors and inorganic photodetectors. Photoluminescence spectra, charge transport properties, and morphology of blend films are investigated to elucidate the influence of polymeric structures on device performances. This contribution demonstrates a strategy of systematically tuning the polymeric structures to achieve high performance all‐polymer photoresponse devices.     

Imide‐Functionalized Heteroarene‐Based n‐Type Terpolymers Incorporating Intramolecular Noncovalent Sulfur∙∙∙Oxygen Interactions for Additive‐Free All‐Polymer Solar Cells

The aggregation/crystallinity of classic n‐type terpolymers based on naphthalene diimide and perylene diimide is challenging to tune due to their rigid and extended cores, leading to suboptimal film morphology. A new strategy for developing high‐performance n‐type terpolymers by incorporating imide‐functionalized heteroarenes is reported here to balance crystallinity and miscibility without sacrificing charge carrier mobilities. The introduction of thienopyrroledione (TPD) into the copolymer f‐BTI2‐FT results in a series of terpolymers BTI2‐xTPD having distinct TPD content. The irregular backbone reduces crystallinity, yielding improved miscibility with the polymer donor. More importantly, TPD triggers noncovalent S?O interactions, increasing backbone planarity and in‐chain charge transport. Such interactions also promote face‐on polymer packing. As a result, all‐polymer solar cells (all‐PSCs) based on BTI2‐30TPD achieve an optimal power conversion efficiency (PCE) of 8.28% with a small energy loss (0.53 eV). This efficiency is substantially higher than that of TPD (4.4%) or a BTI2‐based copolymer (6.8%) and is also the highest for additive‐free all‐PSCs based on a terpolymer acceptor. Moreover, the BTI2‐30TPD cell exhibits excellent stability with the PCE retaining 90% of its initial value after 400 h of aging. The results demonstrate that random polymerization using imide‐functionalized heteroarenes is a powerful approach to develop terpolymer acceptors toward efficient and stable all‐polymer solar cell PSCs.     

Reinforcing the Built‐In Field for Efficient Charge Collection in Polymer Solar Cells

The collection efficiency of photogenerated charges in polymer solar cells (PSCs) is strongly influenced by the built‐in field (E_in) that develops across the photoactive materials. Here, by investigating the E_in‐development regimes in PSCs by introducing two types of interlayers, electric dipole layers (EDLs) and charge transport layers (CTLs), the device architecture is optimized to result in a larger E_in. By incorporating a pair of EDLs on both sides of the photoactive layer, the E_in is modulated by shifting the vacuum energy at each metal–semiconductor interface, providing a larger E_in than that in conventional PSCs using typical CTLs, such as metal oxides and/or conducting polymers. These devices using paired EDLs exhibit an average PCE of 9.8%, which far surpasses the average PCE of ≈8.5% for paired CTLs.