Local Structure-Induced Selective Interactions Enables High-Performance and Burn-in-Free Organic Photovoltaics.

Oligomeric acceptors (OAs) have attracted considerable attention in the organic photovoltaics (OPV) field owing to their capacity in balancing the merits from both monomeric and polymeric acceptors. A delicate control over the distortion between blocks of OAs usually determines the performance and stability of relevant OPV devices. However, it imposes great complexity to realize a controllable degree of distortion by tuning the skeleton of blocks and the position of linker between blocks. Herein, we developed a facile strategy to rationally control the geometry distortion of OAs via a straightforward substitution of alkoxy side-chains on their blocks. This helps elucidate the integrated influences of molecular distortion and non-bonded contacts on the selective interactions between OA molecules and between OA and host acceptor in ternary blend. We demonstrate the alkoxy-OA molecules having stronger self-interactions would mitigate their interactions with host acceptor, therefore alleviating the kinetic diffusion and excessive aggregation of total acceptors. Combining with a composite-interlayer strategy by introducing a phenyl-substituted self-assembled monolayer to enhance the doping with polyoxometalate, an impressive efficiency of 20.1% is achieved accompanied by a negligible burn-in loss against physical aging. This study demonstrates the validation of tuning of selective interactions towards high-performance and burn-in-free OPV.

Single-junction organic solar cells with over 19% efficiency enabled by a refined double-fibril network morphology.

In organic photovoltaics, morphological control of donor and acceptor domains on the nanoscale is the key for enabling efficient exciton diffusion and dissociation, carrier transport and suppression of recombination losses. To realize this, here, we demonstrated a double-fibril network based on a ternary donor-acceptor morphology with multi-length scales constructed by combining ancillary conjugated polymer crystallizers and a non-fullerene acceptor filament assembly. Using this approach, we achieved an average power conversion efficiency of 19.3% (certified 19.2%). The success lies in the good match between the photoelectric parameters and the morphological characteristic lengths, which utilizes the excitons and free charges efficiently. This strategy leads to an enhanced exciton diffusion length and a reduced recombination rate, hence minimizing photon-to-electron losses in the ternary devices as compared to their binary counterparts. The double-fibril network morphology strategy minimizes losses and maximizes the power output, offering the possibility of 20% power conversion efficiencies in single-junction organic photovoltaics.

Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage.

Covalent organic frameworks (COFs) with efficient charge transport and exceptional chemical stability are emerging as an import class of semiconducting materials for opto-/electronic devices and energy-related applications. However, the limited synthetic chemistry to access such materials and the lack of mechanistic understanding of carrier mobility greatly hinder their practical applications. Herein, we report the synthesis of three chemically stable polyarylether-based metallophthalocyanine COFs (PAE-PcM, M = Cu, Ni, and Co) and facile in situ growth of their thin films on various substrates (i.e., SiO2/Si, ITO, quartz) under solvothermal conditions. We show that PAE-PcM COFs thin films with van der Waals layered structures exhibit p-type semiconducting properties with the intrinsic mobility up to ∼19.4 cm2 V-1 s-1 and 4 orders of magnitude of increase in conductivity for PAE-PcCu film (0.2 S m-1) after iodine doping. Density functional theory calculations reveal that the carrier transport in the framework is anisotropic, with the out-of-plane hole transport along columnar stacked phthalocyanine more favorable. Furthermore, PAE-PcCo shows the redox behavior maximumly contributes ∼88.5% of its capacitance performance, giving rise to a high surface area normalized capacitance of ∼19 µF cm-2. Overall, this work not only offers fundamental understandings of electronic properties of polyarylether-based 2D COFs but also paves the way for their energy-related applications.

Efficient Non-Fullerene Organic Solar Cells Based on a Wide-Bandgap Polymer Donor Containing an Alkylthiophenyl-Substituted Benzodithiophene Moiety.

Two wide-bandgap polymer donors containing an alkylthiophenyl substituted benzo[1,2-b : 4,5-b']dithiophene moiety, namely PTZPO and PTZPS, were designed and synthesized. Both polymers exhibit relatively wide optical bandgap of 1.95 V with similar absorption profiles. The polymer PTZPS with alkylthiophenyl substituted benzo[1,2-b : 4,5-b']dithiophene units showed enhanced light-harvesting capabilities, leading to improved short-circuit current densities. The PTZPS : ITIC film shows more appreciable film morphology and phase separation than the film composed of a blend of ITIC with alkoxyl substitutions containing copolymer PTZPO, which facilitates exciton dissociation and charge transport. The PTZPS : ITIC-based non-fullerene organic solar cells show clearly improved short-circuit current density and an impressively high power conversion efficiency of more than 11 %. These observations demonstrate the great promise of using PTZPS as electron-donating materials for high-performance non-fullerene organic solar cells.

Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers.

Jamming Giant Molecules at Interface in Organic Photovoltaics to Improve Performance and Stability.

A novel approach for depositing the giant molecule acceptor (GMA) at the donor-acceptor interface to enhance the efficiency and stability of organic photovoltaic (OPV) devices through a designed interface-enhanced layer-by-layer device fabrication protocol is proposed. The giant molecule acceptor DQx-Ph is mixed with the polymer donor in the bottom layer to form a polymer donor fibril phase and a mixed phase, followed by subsequent deposition of the main acceptor L8-BO. The L8-BO solution swells the bottom layer and alters the localized morphology of the mixing phase, introducing L8-BO fibrillar crystallization and pushing DQx-Ph giant molecules outwards to the fibril interfaces. Through this approach, the localized morphology and optoelectronic property of the bulk heterojunction are optimized. This configuration maintains the superior transport properties of L8-BO while integrating the high open-circuit voltage characteristics of DQx-Ph. Additionally, exciton dissociation and charge generation are simultaneously enhanced, with suppressed energy losses. A power conversion efficiency of 19.9% with improved operational stability is achieved, underscoring the importance of GMA interface jamming in advancing OPV technology. This study provides new insights into the development of ancillary OPV materials to overcome the critical limitations in OPV, revealing innovative approaches for photovoltaic technologies.

High-temperature low-humidity proton exchange membrane with "stream-reservoir" ionic channels for high-power-density fuel cells.

The perfluorosulfonic acid (PFSA) proton exchange membrane (PEM) is the key component for hydrogen fuel cells (FCs). We used in situ synchrotron scattering to investigate the PEM morphology evolution and found a "stream-reservoir" morphology, which enables efficient proton transport. The short-side-chain (SSC) PFSA PEM is fabricated under the guidance of morphology optimization, which delivered a proton conductivity of 193 milliSiemens per centimeter [95% relativity humidity (RH)] and 40 milliSiemens per centimeter (40% RH) at 80°C. The improved glass transition temperature, water permeability, and mechanical strength enable high-temperature low-humidity FC applications. Performance improvement by 82.3% at 110°C and 25% RH is obtained for SSC-PFSA PEM FCs compared to Nafion polymer PEM devices. The insights in chain conformation, packing mechanism, crystallization, and phase separation of PFSAs build up the structure-property relationship. In addition, SSC-PFSA PEM is ideal for high-temperature low-humidity FCs that are needed urgently for high-power-density and heavy-duty applications.

Understanding the Role of Removable Solid Additives: Selective Interaction Contributes to Vertical Component Distributions.

Sequentially deposited organic solar cells (SD-OSCs) have attracted great attention owing to their ability in achieving a more favorable, vertically phase-separated morphology to avoid the accumulation of counter charges at absorber/transporting layer interfaces. However, the processing of SD-OSCs is still quite challenging in preventing the penetration of small-molecule acceptors into the polymer donor layer via erosion or swelling. Herein, solid additives (SAs) with varied electrostatic potential distributions and steric hinderance are introduced into SD-OSCs to investigate the effect of evaporation dynamics and selective interaction on vertical component distribution. Multiple modelings indicate that the π-π interaction dominates the interactions between aromatic SAs and active layer components. Among them, p-dibromobenzene shows a stronger interaction with the donor while 2-chloronaphthalene (2-CN) interacts more preferably with acceptor. Combining the depth-dependent morphological study aided by multiple X-ray scattering methods, it is concluded that the evaporation of SAs can drive the stronger-interaction component upward to the surface, while having minor impact on the overall molecular packing. Ultimately, the 2-CN-treated devices with reduced acceptor concentration at the bottom surface deliver a high power conversion efficiency of 19.2%, demonstrating the effectiveness of applying selective interactions to improve the vertical morphology of OSCs by using SAs with proper structure.

Mastering morphology of non-fullerene acceptors towards long-term stable organic solar cells.

Despite the rapid progress of organic solar cells based on non-fullerene acceptors, simultaneously achieving high power conversion efficiency and long-term stability for commercialization requires sustainable research effort. Here, we demonstrate stable devices by integrating a wide bandgap electron-donating polymer (namely PTzBI-dF) and two acceptors (namely L8BO and Y6) that feature similar structures yet different thermal and morphological properties. The organic solar cell based on PTzBI-dF:L8BO:Y6 could achieve a promising efficiency of 18.26% in the conventional device structure. In the inverted structure, excellent long-term thermal stability over 1400 h under 85 °C continuous heating is obtained. The improved performance can be ascribed to suppressed charge recombination along with appropriate charge transport. We find that the morphological features in terms of crystalline coherence length of fresh and aged films can be gradually regulated by the weight ratio of L8BO:Y6. Additionally, the occurrence of melting point decrease and reduced enthalpy in PTzBI-dF:L8BO:Y6 films could prohibit the amorphous phase to cluster, and consequently overcome the energetic traps accumulation aroused by thermal stress, which is a critical issue in high efficiency non-fullerene acceptors-based devices. This work provides insight into understanding non-fullerene acceptors-based organic solar cells for improved efficiency and stability.

All-polymer organic solar cells with nano-to-micron hierarchical morphology and large light receiving angle.

Distributed photovoltaics in living environment harvest the sunlight in different incident angles throughout the day. The development of planer solar cells with large light-receiving angle can reduce the requirements in installation form factor and is therefore urgently required. Here, thin film organic photovoltaics with nano-sized phase separation integrated in micro-sized surface topology is demonstrated as an ideal solution to proposed applications. All-polymer solar cells, by means of a newly developed sequential processing, show large magnitude hierarchical morphology with facilitated exciton-to-carrier conversion. The nano fibrilar donor-acceptor network and micron-scale optical field trapping structure in combination contributes to an efficiency of 19.06% (certified 18.59%), which is the highest value to date for all-polymer solar cells. Furthermore, the micron-sized surface topology also contributes to a large light-receiving angle. A 30% improvement of power gain is achieved for the hierarchical morphology comparing to the flat-morphology devices. These inspiring results show that all-polymer solar cell with hierarchical features are particularly suitable for the commercial applications of distributed photovoltaics due to its low installation requirement.

Highly Efficient Organic Solar Cells Enabled by the Incorporation of a Sulfonated Graphene Doped PEDOT:PSS Interlayer.

An interface modification layer plays an important role in improving the performance of organic solar cells (OSCs). The structure design or doping of electrode interlayer materials can effectively inhibit interfacial carrier recombination and improve ohmic contact between the active layer and the electrodes, which is desirable for realizing high power conversion efficiencies (PCEs). Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been extensively used as a hole-transport layer (HTL) in OSCs. Here, a modification of PEDOT:PSS is proposed using sulfonated graphene (SG) as a secondary dopant for improving the surface morphology and conductivity. The incorporation of the SG-doped PEDOT:PSS as the HTLs in OSCs leads to the increased charge extraction and shows the best PCEs of 17.48% for PM6:Y6 devices and 18.56% for PM6:L8-BO devices. The significant improvement in device performance suggests that SG-PEDOT:PSS is a promising interfacial layer for efficient charge transport and extraction toward high-efficiency OSCs.

Decoupling Complex Multi-Length-Scale Morphology in Non-Fullerene Photovoltaics with Nitrogen K-Edge Resonant Soft X-ray Scattering.

Complex morphology in organic photovoltaics (OPVs) and other functional soft materials commonly dictates performance. Such complexity in OPVs originates from the mesoscale kinetically trapped non-equilibrium state, which governs device charge generation and transport. Resonant soft X-ray scattering (RSoXS) has been revolutionary in the exploration of OPV morphology in the past decade due to its chemical and orientation sensitivity. However, for non-fullerene OPVs, RSoXS analysis near the carbon K-edge is challenging, due to the chemical similarity of the materials used in active layers. An innovative approach is provided by nitrogen K-edge RSoXS (NK-RSoXS), utilizing the spatial and orientational contrasts from the cyano groups in the acceptor materials, which allows for determination of phase separation. NK-RSoXS clearly visualizes the combined feature sizes in PM6:Y6 blends from crystallization and liquid-liquid demixing, while PM6:Y6:Y6-BO ternary blends with reduced phase-separation size and enhanced material crystallization can lead to current amplification in devices. Nitrogen is common in organic semiconductors and other soft materials, and the strong and directional N 1s → π* resonances make NK-RSoXS a powerful tool to uncover the mesoscale complexity and open opportunities to understand heterogeneous systems.

Correlating Electronic Structure and Device Physics with Mixing Region Morphology in High-Efficiency Organic Solar Cells.

The donor/acceptor interaction in non-fullerene organic photovoltaics leads to the mixing domain that dictates the morphology and electronic structure of the blended thin film. Initiative effort is paid to understand how these domain properties affect the device performances on high-efficiency PM6:Y6 blends. Different fullerenes acceptors are used to manipulate the feature of mixing domain. It is seen that a tight packing in the mixing region is critical, which could effectively enhance the hole transfer and lead to the enlarged and narrow electron density of state (DOS). As a result, short-circuit current (JSC ) and fill factor (FF) are improved. The distribution of DOS and energy levels strongly influences open-circuit voltage (VOC ). The raised filling state of electron Fermi level is seen to be key in determining device VOC . Energy disorder is found to be a key factor to energy loss, which is highly correlated with the intermolecular distance in the mixing region. A 17.53% efficiency is obtained for optimized ternary devices, which is the highest value for similar systems. The current results indicate that a delicate optimization of the mixing domain property is an effective route to improve the VOC , JSC , and FF simultaneously, which provides new guidelines for morphology control toward high-performance organic solar cells.

Design Rules of the Mixing Phase and Impacts on Device Performance in High-Efficiency Organic Photovoltaics.

In nonfullerene acceptor- (NFA-) based solar cells, the exciton splitting takes place at both domain interface and donor/acceptor mixture, which brings in the state of mixing phase into focus. The energetics and morphology are key parameters dictating the charge generation, diffusion, and recombination. It is revealed that tailoringthe electronic properties of the mixing region by doping with larger-bandgap components could reduce the density of state but elevate the filling state level, leading to improved open-circuit voltage (V OC) and reduced recombination. The monomolecular and bimolecular recombinations are shown to be intercorrelated, which show a Gaussian-like relationship with V OC and linear relationship with short-circuit current density (J SC) and fill factor (FF). The kinetics of hole transfer and exciton diffusion scale with J SC similarly, indicating the carrier generation in mixing region and crystalline domain are equally important. From the morphology perspective, the crystalline order could contribute to V OC improvement, and the fibrillar structure strongly affects the FF. These observations highlight the importance of the mixing region and its connection with crystalline domains and point out the design rules to optimize the mixing phase structure, which is an effective approach to further improve device performance.

Probing morphology and chemistry in complex soft materials within situresonant soft x-ray scattering.

Small angle scattering methodologies have been evolving at fast pace over the past few decades due to the ever-increasing demands for more details on the complex nanostructures of multiphase and multicomponent soft materials like polymer assemblies and biomaterials. Currently, element-specific and contrast variation techniques such as resonant (elastic) soft/tender x-ray scattering, anomalous small angle x-ray scattering, and contrast-matching small angle neutron scattering, or combinations of above are routinely used to extract the chemical composition and spatial arrangement of constituent elements at multiple length scales and examine electronic ordering phenomena. Here we present some recent advances in selectively characterizing structural architectures of complex soft materials, which often contain multi-components with a wide range of length scales and multiple functionalities, where novel resonant scattering approaches have been demonstrated to decipher a higher level of structural complexity that correlates to functionality. With the advancement of machine learning and artificial intelligence assisted correlative analysis, high-throughput and autonomous experiments would open a new paradigm of material research. Further development of resonant x-ray scattering instrumentation with crossplatform sample environments will enable multimodalin situ/operando characterization of the system dynamics with much improved spatial and temporal resolution.

Constructing a new polymer acceptor enabled non-halogenated solvent-processed all-polymer solar cell with an efficiency of 13.8.

A new polymer acceptor, PS1, was developed by connecting the non-fullerene acceptor building block of dithienothiophen[3,2-b]pyrrolobenzotriazole capped with 3-(dicyanomethylidene)-indan-1-one through a thiophene spacer. The solubilizing alkyl side groups in the central unit enabled PS1 to be readily dissolved in non-chlorinated solvents. By using 2-methyltetrahydrofuran as the processing solvent, the all-polymer solar cell (all-PSC) containing PS1 and a polymer donor PTzBI-oF in the light-harvesting layer exhibited an impressively high power conversion efficiency of 13.8%.

Capture the high-efficiency non-fullerene ternary organic solar cells formula by machine-learning-assisted energy-level alignment optimization.

Appropriate energy-level alignment in non-fullerene ternary organic solar cells (OSCs) can enhance the power conversion efficiencies (PCEs), due to the simultaneous improvement in charge generation/transportation and reduction in voltage loss. Seven machine-learning (ML) algorithms were used to build the regression and classification models based on energy-level parameters to predict PCE and capture high-performance material combinations, and random forest showed the best predictive capability. Furthermore, two sets of verification experiments were designed to compare the experimental and predicted results. The outcome elucidated that a deep lowest unoccupied molecular orbital (LUMO) of the non-fullerene acceptors can slightly reduce the open-circuit voltage (V OC) but significantly improve short-circuit current density (J SC), and, to a certain extent, the V OC could be optimized by the slightly up-shifted LUMO of the third component in non-fullerene ternary OSCs. Consequently, random forest can provide an effective global optimization scheme and capture multi-component combinations for high-efficiency ternary OSCs.

Improving the Electroluminescent Performance of Blue Light-Emitting Polymers by Side-Chain Modification.

Blue light-emitting polymers are in urgent demand for new-generation display and solid-state lighting devices fabricated through low-cost wet processing. However, their current performances are far from satisfactory. Here, we developed a series of poly(fluorene-co-dibenzothiophene-S,S-dioxides) (PFSOs) bearing different alkyl chains, alkoxyphenyl chains, or both alkylaryl and alkoxyphenyl side chains. The introduction of alkoxyphenyl groups moderately enhanced the electron-donating ability of the polymers, leading to more balanced charge carrier fluxes. Meanwhile, asymmetric bulky side chains enabled more pronounced variation of molecular conformation while restraining the intermolecular aggregation of polymers, resulting in a lower refractive index, thus facilitating light extraction compared with polymers based on the same two alkyl or alkoxyphenyl side chains. Polymer light-emitting devices based on PFSO-BMD with asymmetric side chains exhibited a maximum luminous efficiency of 8.58 cd A-1, associated with pure blue Commission Internationale de l'Eclairage coordinates of (0.14, 0.14). These findings demonstrated that side-chain modification can be an effective strategy for developing efficient solution-processable blue light-emitting polymers.

Design and synthesis of non-fullerene acceptors based on a quinoxalineimide moiety as the central building block for organic solar cells.

Two new non-fullerene acceptors, namely QIP-4F and QIP-4Cl, containing a novel imide-functionalized quinoxaline (QI) moiety fused with a thienylthiophene unit as the central building block, and fluorinated or chlorinated 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile as end-capping groups, were designed and synthesized, respectively. An optimized device based on P2F-EHp:QIP-4Cl presented a power conversion efficiency of 13.3%, with an impressively high open-circuit voltage of 0.94 V. These results demonstrate the great potential of QI-containing fused units as central building blocks for high-performance acceptors.

Surpassing the 10% efficiency milestone for 1-cm2 all-polymer solar cells.

Naphthalenediimide-based n-type polymeric semiconductors are extensively used for constructing high-performance all-polymer solar cells (all-PSCs). For such all-polymer systems, charge recombination can be reduced by using thinner active layers, yet suffering insufficient near-infrared light harvesting from the polymeric acceptor. Conversely, increasing the layer thickness overcomes the light harvesting issue, but at the cost of severe charge recombination effects. Here we demonstrate that to manage light propagation within all-PSCs, a thick bulk-heterojunction film of approximately 350 nm is needed to effectively enhance photo-harvesting in the near-infrared region. To overcome the severe charge recombination in such a thick film, a non-halogenic additive is used to induce a well-ordered micro-structure that inherently suppresses recombination loss. The combined strategies of light management and delicate morphology optimization lead to a promising efficiency over 10% for thick-film all-PSCs with active area of 1 cm2, showing great promise for future large-scale production and application of all-PSCs.